Certain 2-(2-chloro-3-alkoxy-4-substituted benzoyl)-5-methyl-5-1,3-cyclohexanediones as herbicides

ABSTRACT

Herbicidal compounds of the formula ##STR1## wherein R 3  is methoxy or ethoxy; and 
     R 4  is bromine, methylsulfonyl or ethylsulfonyl 
     and their salts.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of Ser. No. 07/128,128,filed Feb. 23, 1988, now U.S. Pat. No. 5,006,158 which is a divisionalapplication of Ser. No. 06/880,370, filed June 30, 1986, now U.S. Pat.No. 4,780,127 which is a continuation-in-part applicattion of Ser. No.772,593, filed Sept. 5, 1985, now abandoned; which in turn is acontination-in-part application of Ser. No. 634,408, filed July 31,1984, now abandoned; which in turn is a contination-in-part applicationof Ser. No. 587,331, filed Mar. 7, 1984, now abandoned; which in turn isa continuation-in-part application of Ser. No. 532,869, filed Sept. 16,1983, now abandoned; which in turn is a continuation-in-part applicationof Ser. No. 464,251, filed Feb. 9, 1983, now abandoned; which in turn isa continuation-in-part application of Ser. No. 361,658, filed Mar. 25,1982, now abandoned.

BACKGROUND OF THE INVENTION

Compounds having the structural formula ##STR2## wherein X can be alkyl,n can be 0, 1, or 2, and R₁ can be phenyl or substituted phenyl aredescribed in Japanese Patent Application 84632-1974 as beingintermediates for the preparation of herbicidal compounds of the formula##STR3## wherein R₁, X, and n are as defined above and R₂ is alkyl,alkenyl, or alkynyl. Specifically taught herbicidal compounds of thislatter group are those where n is 2, X is 5,5-dimethyl, R₂ is allyl andR₁ is phenyl, 4-chlorophenyl or 4-methoxyphenyl.

The precursor intermediates for these three specifically taughtcompounds have no or almost no herbicidal activity.

DESCRIPTION OF THE INVENTION

Embodiment A of this invention relates to certain novel 2-(2-substitutedbenzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of thisembodiment have the following structural formula ##STR4## wherein

R and R¹ are hydrogen, C₁ -C₄ alkyl, preferably methyl or isopropyl,R^(a) OC(O)-, where R^(a) is C₁ -C₄ alkyl; most preferably R and R¹ arehydrogen;

R² is chlorine, bromine, iodine or C₁ -C₄ alkoxy, preferably methoxy;most preferably R₂ is chlorine, bromine or methoxy;

R³, R⁴ and R⁵ independently are hydrogen or an aliphatic group,preferably: (1) hydrogen; (2) halogen, preferably chlorine or bromine;(3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ alkoxy, preferablymethoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C₁ -C₄haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n) -- whereinR^(b) is C₁ -C₄ alkyl, preferably methyl, C₁ -C₄ haloalkyl, phenyl,benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently arehydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2, preferably 2;##STR5## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen or C₁ -C₄alkyl, preferably methyl; (11) R^(f) C(O) wherein R^(f) is hydrogen, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; (12) --NR^(g) R^(h) whereinR^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; or lesspreferably (13) R³ and R⁴ together can form a ring structure with twoadjacent carbon atoms of the phenyl ring.

R³ and R⁴ can also be (14) C₃ -C₅ alkenyloxy (thio) optionallysubstituted, preferably with halogen or (15) C₃ -C₅ alkynyloxy (thio),optionally substituted, preferably with halogen.

Most preferably, R³ is chlorine, hydrogen, dimethylamino or methoxy.Preferably, R⁴ is hydrogen, chlorine, nitro, SO₂ CH₃, SO₂ N(CH₃)₂ ortrifluoromethyl. Preferably, R⁵ is hydrogen.

Embodiment A' of this invention is an herbicidal composition comprisingan herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inertcarrier threfor. Preferably, the 2-position of the benzoyl moiety issubstituted with chlorine, bromine, iodine or C₁ -C₄ alkoxy; morepreferably chlorine, bromine or methoxy; most preferably chlorine. The5-position of the 1,3-cyclohexanedione moiety can be substituted withone or two C₁ -C₄ alkyl groups, preferably methyl, although such asubstitution is not preferred.

The compounds of Embodiment A of this invention can have the followingfour structural formulae because of tautomerism: ##STR6## wherein R, R¹,R², R³, R⁴ and R⁵ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR7## whereinR, R¹, R², R³, R⁴ and R⁵ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals, e.g. lithium, sodium, and potassium, alkaline earth metals, e.g.barium, magnesium, calcium and strontium or organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substituentis an aliphatic or aromatic group.

In the above description of the compounds of this invention, alkyl andalkoxy include both straight and branched configurations; for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, andtert-butyl.

Embodiment B of this invention relates to certain novel 2-(2-substitutedbenzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of thisembodiment have the following structural formula ##STR8## wherein

R¹⁰ is C₁ -C₆ alkyl, preferably C₁ -C₄, more preferably methyl;

R¹¹ is hydrogen or C₁ -C₆ alkyl, preferably C₁ -C₄, more preferablymethyl or ##STR9## wherein R^(a) is C₁ -C₄ alkyl or R¹⁰ and R¹¹ togetherare alkylene having 3 to 6 carbon atoms, most preferably R¹¹ is hydrogenor methyl;

R¹² is chlorine, bromine, iodine, fluorine or C₁ -C₄ alkoxy, preferablymethoxy; most preferably R¹² is chlorine, bromine or methoxy;

R¹³ and R¹⁴ independently are (1) hydrogen or an aliphatic group,preferably hydrogen; (2) halogen, preferably, fluorine, chlorine orbromine; (3) C₁ -C₄ alkyl, preferably methyl; (4) C₁ -C₄ aliphaticalkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro;(8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b) SO_(n)-- wherein R^(b) is C₁ -C₄ alkyl, preferably methyl, C₁ -C₄ haloalkyl,phenyl, benzyl, --NR^(d) R^(e) wherein R^(d) and R^(e) independently arehydrogen or C₁ -C₄ alkyl; and n is the integer 0, 1 or 2, preferably 2;##STR10## wherein R^(c) is C₁ -C₄ alkyl and R^(j) is hydrogen or C₁ -C₄alkyl, preferably methyl; (11) R^(f) C(O) wherein R^(f) is hydrogen, C₁-C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy; (12) --NR^(g) R^(h) whereinR^(g) and R^(h) independently are hydrogen or C₁ -C₄ alkyl; (13) C₁ -C₄alkylthio or less preferably (14) R¹³ and R¹⁴ together can form a ringstructure with two adjacent carbon atoms of the phenyl ring to whichthey are attached or less preferably (15) R¹³ and R¹⁴ are the groupsphenoxy or substituted phenoxy wherein the substituent is halogen orhalomethyl or both;

R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are independently the same or different and areselected from the group consisting of hydrogen, C₁ -C₆ alkyl, preferablyC₁ -C₄ alkyl, more preferably methyl, most preferably hydrogen ormethyl, and their salts;

provided, however, that R¹⁵ and R¹⁶ together may form a substituted orunsubstituted alkylene ring of 2-5 carbon atoms, the preferredsubstituent being 1 or 2 methyl groups.

More preferably, R¹³ is chlorine, hydrogen, methyl, alkylthio ormethoxy. Preferably R¹⁴ is hydrogen, chlorine, nitro, trifluoromethyl,or R^(b) SO_(n) wherein R^(b) is C₁ -C₄ alkyl, preferably methyl and nis the integer 0, 1 or 2, preferably 2.

The compounds of Embodiment B of this invention can have the followingfour structural formulae because of tautomerism: ##STR11## wherein R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR12## whereinR¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium, alkaline earth metals, e.g.barium, magnesium, calcium and strontium, or organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substitutentis an aliphatic or aromatic group.

The term "aliphatic group" is used form Embodiments A and B herein in abroad sense to cover a large class of organic groups characterized bybeing derived from (1) an acylic (open-chain structure) of the paraffin,olefin and acetylene hydrocarbon series and their derivatives or (2)alicyclic compounds. The aliphatic group can have from 1 to 10 carbonatoms.

The term "aromatic group" is used for Embodiments A and B herein in abroad sense to distinguish from the aliphatic group and includes a groupderived from (1) compounds having 6 to 20 carbon atoms and characterizedby the presence of at least one benzene ring, including monocyclic,bicyclic and polycyclic hydrocarbons and their derivatives and (2)heterocyclic compounds having 5 to 19 carbon atoms which are similar instructure and are characterized by having an unsaturated ring structurecontaining at least one atom other than carbon such as nitrogen, sulfurand oxygen and derivatives of these heterocyclic compounds.

In the above description of the compounds of this invention alkyl andalkoxy include both straight and branched configurations; for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, andtert-butyl.

Embodiment C of this invention relates to certain novel2-(2'-cyanobenzoyl)cyclohexane-1,3-diones as herbicides. The compoundsof of this embodiment have the following structural formula ##STR13##wherein R²¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R²¹ is hydrogen or methyl;

R²² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR14## wherein R^(a) is C₁ -C₄ alkyl, most preferably R²²is hydrogen or methyl; or R²¹ and R²² together are alkylene having 3 to6 carbon atoms;

R²³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R²³ is hydrogen or methyl;

R²⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R²⁴ is hydrogen or methyl;

R²⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R²⁵ is hydrogen or methyl;

R²⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R²⁶ is hydrogen;

R²⁷ and R²⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are asdefined, with the proviso that R²⁷ is not attached to the 6-position.

Preferably, R²⁷ is in the 3-position. Most preferably R²⁷ is hydrogenand R²⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, orR^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this embodiment can have the following four structuralformulae because of tautomerism: ##STR15## wherein R²¹, R²², R²³, R²⁴,R²⁵, R²⁶, R²⁷ and R²⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR16## whereinR²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ are as defined above.

Examples of cations of these bases are inorgaic cations such as alkalimetals e.g. lithium, sodium, and potassium organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substitutentis an aliphatic or aromatic group.

Embodiment D of this invention relates to2-(2-nitrobenzoyl)-1,3-cyclohexanediones and their use as herbicides.

The compounds have a nitro substitution in the 2-position of the phenylmoiety of their compounds. The nitro substitution imparts exceptionalherbicidal activity to the compounds of this invention.

Embodiment D' of this invention is an herbicidal composition comprisingan herbicidally active 2-(2-nitrobenzoyl)-1,3-cyclohexanedione and aninert carrier therefor. The 4-, 5- and 6-positions of the1,3-cyclohexanedione moiety can be substituted, preferably with thegroups hereinafter recited. More preferably, the 1,3-cyclohexanedionemoiety has no substitution or the 4- or 6-positions are substituted withone or two methyl groups. The 3-, 4- and 5-positions of the benzoylmoiety can be substituted, preferably with the groups hereinafterrecited.

The novel compounds of Embodiment D have the following structuralformula ##STR17## wherein R³¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁-C₂ alkyl, more preferably methyl, most preferably R³¹ is hydrogen ormethyl;

R³² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR18## wherein R^(a) is C₁ -C₄ alkyl, most preferably R³²is hydrogen or methyl;

R³¹ and R³² together are alkylene having 3 to 6 carbon atoms;

R³³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R³³ is hydrogen or methyl;

R³⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R³⁴ is hydrogen or methyl;

R³⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R³⁵ is hydrogen or methyl;

R³⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R³⁶ is hydrogen;

R³⁷ and R³⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are asdefined, with the proviso that R³⁷ is not attached to the 6-position.

Preferably, R³⁷ is in the 3-position. Most preferably R³⁷ is hydrogen orC₁ -C₄ alkoxy and R³⁸ is hydrogen, chlorine, bromine, fluorine,trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferablymethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkylgroups with one or more hydrogens replaced by chlorine, bromine, iodineor fluorine.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR19## wherein R³¹, R³², R³³, R³⁴,R³⁵, R³⁶, R³⁷ and R³⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR20## whereinR³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷ and R³⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium or organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substitutentis an aliphatic or aromatic group.

Embodiment E of this invention relates to2-(2-benzoyl)-1,3-cyclohexanediones and their use as herbicides.

Embodiment E' of this invention is an herbicidal composition comprisingan herbicidally active 2-(2-C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl or C₁-C₄ alkylsulfonyl benzoyl)-1,3-cyclohexanedione and an inert carriertherefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moietycan be substituted, preferably with the groups hereinafter recited. Morepreferably, the 1,3-cyclohexanedione moiety has no substitution or the4- or 6-positions are substituted with one or two methyl groups. The 3-,4- and 5-positions of the benzoyl moiety can be substituted, preferablywith the groups hereinafter recited.

The novel compounds of Embodiment E have the structural formula##STR21## wherein n is the interger 0, 1 or 2, preferably 2;

R⁴⁰ is C₁ -C₄ alkyl, preferably methyl;

R⁴¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁴¹ is hydrogen or methyl;

R⁴² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR22## wherein R^(a) is C₁ -C₄ alkyl, most preferably R⁴²is hydrogen or methyl; or

R⁴¹ and R⁴² together are alkylene having 3 to 6 carbon atoms;

R⁴³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁴³ is hydrogen or methyl;

R⁴⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁴⁴ is hydrogen or methyl;

R⁴⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁴⁵ is hydrogen or methyl;

R⁴⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁴⁶ is hydrogen;

R⁴⁷ and R⁴⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkoxy; or(12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are as defined, with theproviso that R⁴⁷ is not attached to the 6-position.

Preferably, R⁴⁷ is in the 3-position. Most preferably R⁴⁷ is hydrogen or3-chlorine and R⁴⁸ is hydrogen, chlorine, bromine, fluorine,trifluoromethyl, or R^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferablymethyl.

The term "C₁ -C₄ " alkyl includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkylgroups with one or more hydrogens replaced by chloro, bromo, iodo orfluoro.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR23## wherein n, R⁴⁰, R⁴¹, R⁴²,R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR24## whereinn, R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷ and R⁴⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium, organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substituentis an aliphatic or aromatic group.

Embodiment F of this invention relates to2-(2-alkylbenzoyl)-1,3-cyclohexanediones and their use as herbicides.

Embodiment F' of this invention is an herbicidal composition comprisingan herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inertcarrier therefor wherein the 2-position of the benzoyl moiety issubstituted with C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, optionallysubstituted with halogen, more preferably methyl or trifluoromethyl andthe 4-position preferably is substituted with an electron withdrawinggroup, such as halogen, cyano, trifluoromethyl or nitro. The 4-, 5- and6-positions of the 1,3-cyclohexanedione moiety can be substituted,preferably with the groups hereinafter recited. More preferably, the1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positionsare substituted with one or two methyl groups. The 3-, 4- and5-positions of the benzoyl moiety can be substituted, preferably withthe groups hereinafter recited.

The novel compounds of Embodiment F have the following structuralformula ##STR25## wherein R⁵⁰ is C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl,optionally substituted with halogen, more preferably methyl andtrifluoromethyl;

R⁵¹ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁵¹ is hydrogen or methyl;

R⁵² is hydrogen; C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, more preferablymethyl or ##STR26## wherein R^(a) is C₁ -C₄ alkyl, most preferably R⁵²is hydrogen or methyl; or

R⁵¹ and R⁵² together are alkylene having 3 to 6 carbon atoms;

R⁵³ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁵³ is hydrogen or methyl;

R⁵⁴ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁵⁴ is hydrogen or methyl;

R⁵⁵ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl; most preferably R⁵⁵ is hydrogen or methyl;

R⁵⁶ is hydrogen or C₁ -C₄ alkyl, preferably C₁ -C₂ alkyl, morepreferably methyl, most preferably R⁵⁶ is hydrogen;

R⁵⁷ and R⁵⁸ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; or (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are asdefined, with the proviso that R⁵⁷ is not attached to the 6-position.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The term "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkylgroups with one or more hydrogens replaced by chloro, bromo, iodo orfluoro.

Preferably, R⁵⁷ is in the 3-position. Most preferably R⁵⁷ is hydrogenand R⁵⁸ is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, orR^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl.

Salts of the above-described compounds (as defined hereinafter) are alsothe subject of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR27## wherein R⁵⁰, R⁵¹, R⁵², R⁵³,R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷ and R⁵⁸ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by any base to give a salthaving an anion of the following four resonance forms: ##STR28## whereinR⁵⁰, R⁵¹, R⁵², R⁵³ R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷ and R⁵⁸ are as defined above.

Examples of cations of these bases are inorganic cations such as alkalimetals e.g. lithium, sodium, and potassium organic cations such assubstituted ammonium, sulfonium or phosphonium wherein the substituentis an aliphatic or aromatic group.

Embodiment G of this invention relates to2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.

Embodiment G' of this invention is an herbicidal composition comprisingan herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione andan inert carrier therefor. The 4- and 6-positions of the1,3,5-cyclohexanetrione moiety are preferably substituted with groupshereinafter defined, most preferably with all methyl groups. The benzoylmoiety can be substituted, preferably with the groups hereinafterrecited.

The novel compounds of Embodiment G have the following structuralformula ##STR29## wherein R⁶⁰ is hydrogen; halogen; C₁ -C₂ alkyl,preferably methyl; C₁ -C₂ alkoxy, preferably methoxy; nitro; cyano; C₁-C₂ haloalkyl, preferably trifluoromethyl; R^(a) SO_(n) -- wherein n is0 or 2, preferably 2 and R^(a) is C₁ -C₂ alkyl, preferably methyl,trifluoromethyl or difluoromethyl; or trifluoromethoxy ordifluoromethoxy. Preferably, R⁶⁰ is chlorine, bromine, C₁ -C₂ alkyl, C₁-C₂ alkoxy, trifluoromethyl, cyano, nitro, C₁ -C₂ alkylthio or C₁ -C₂alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethylor methylsulfonyl; and

R⁶¹ is hydrogen or C₁ -C₄ alkyl, preferably methyl;

R⁶² is hydrogen or C₁ -C₄ alkyl, preferably methyl; or

R⁶¹ and R⁶² together are C₂ -C₅ alkylene;

R⁶³ is C₁ -C₄ alkyl, preferably methyl;

R⁶⁴ is C₁ -C₄ alkyl, preferably methyl; or

R⁶³ and R⁶⁴ together are C₂ -C₅ alkylene;

R⁶⁵ and R⁶⁶ independently are (1) hydrogen; (2) halogen, preferablychlorine, fluorine or bromine; (3) C₁ -C₄ alkyl, preferably methyl; (4)C₁ -C₄ alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7)nitro; (8) C₁ -C₄ haloalkyl, more preferably trifluoromethyl; (9) R^(b)SO_(n) -- wherein n is the integer 0, 1 or 2, preferably 2; and

R^(b) is

(a) C₁ -C₄ alkyl, preferably methyl;

(b) C₁ -C₄ alkyl substituted with halogen or cyano, preferablychloromethyl, trifluoromethyl or cyanomethyl;

(c) phenyl; or

(d) benzyl;

(10) --NR^(c) R^(d) wherein R^(c) and R^(d) independently are hydrogenor C₁ -C₄ alkyl; (11) R^(e) C(O)- wherein R^(e) is C₁ -C₄ alkyl or C₁-C₄ alkoxy; (12) --SO₂ NR^(c) R^(d) wherein R^(c) and R^(d) are asdefined; or (13) --N(R^(c))C(O)R^(d) wherein R^(c) and R^(d) are asdefined.

Preferably R⁶⁵ is in the 3-position. More preferably R⁶⁵ is hydrogen,chlorine, fluorine, trifluoromethyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄thioalkyl. Most preferably, R⁶⁵ is hydrogen. Preferably R⁶⁶ is in the4-position. Most preferably R⁶⁶ is halogen, cyano, trifluoromethyl, orR^(b) SO₂ wherein R^(b) is C₁ -C₄ alkyl, preferably methyl or C₁ -C₄haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.

The term "C₁ -C₄ alkyl" includes methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includeschlorine, bromine, iodine and fluorine. The terms "C₁ -C₄ alkoxy"includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,isobutoxy and t-butoxy. The term "C₁ -C₄ haloalkyl" includes the alkylgroups defined above under C₁ -C₄ alkyl in which one or more hydrogensis replaced by chlorine, bromine, iodine or fluorine.

Salts of the above-described compounds (as defined hereinafter) areincluded within the scope of the instant invention.

The compounds of this invention can have the following four structuralformulae because of tautomerism: ##STR30## wherein R⁶⁰, R⁶¹, R⁶², R⁶³,R⁶⁴, R⁶⁵ and R⁶⁶ are as defined above.

The circled proton on each of the four tautomers is reasonably labile.These protons are acidic and can be removed by reaction with a base toform a salt having an anion of the following four resonance forms:##STR31## wherein R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are as definedabove.

Examples of cations of these bases are inorganic cations such asalkalimetals, e.g., lithium, sodium and potassium; the alkaline earthmetals, e.g. calcium and magnesium or ammonium or organic cations suchas substituted ammonium, sulfonium, sulfoxonium or phosphonium whereinthe substituents are aliphatic or aromatic groups.

Those skilled in the art will recognize in considering the salts of thisinvention that varying degrees os association between the anion andcation will exist depending upon the nature of the cation. In someinstances with a suitable cation, such as copper, the salt can exist ina chelated form.

The compounds of this invention and their salts are active herbicides ofa general type. That is, they are herbicidally effective against a widerange of plant species. The method of controlling undesirable vegetationof the present invention comprises applying an herbicidally effectiveamount of the above-described compounds to the area where control isdesired.

The compounds of Embodiments A and A' of the present invention can beprepared by the following general method. ##STR32##

Generally, mole amounts of the dione and substituted benzoyl cyanide areused, along with a slight mole excess of zinc chloride. The tworeactants and the zinc chloride are combined in a solvent such asmethylene chloride. A slight mole excess of triethylamine is slowlyadded to the reaction mixture with cooling. The mixture is stirred atroom temperature for 5 hours.

The reaction product is worked up by conventional techniques.

The above-described substituted benzoyl cyanide can be preparedaccording to the teaching of T. S. Oakwood and C. A. Weisgerber, OrganicSynthesis Collected, Vol. III, pp. 122 (1955).

The following example teaches the synthesis of a representative compoundof Embodiments A and A' of this invention.

EXAMPLE 1-A,A' 2- (2,4-Dichlorobenzoyl)-cyclohexane-1,3-dione ##STR33##

1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole)2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powderedzinc chloride were combined in 100 milliliters (ml) methylene chloride.Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. Thereaction mixture was stirred at room temperature for 5 hours and thenpoured into 2N hydrochloric acid. The aqueous phase was discarded andthe organic phase was washed with 150 ml 5% Na₂ CO₃ four times. Theaqueous washings were combined and acidified with HCl, extracted withmethylene chloride, dried and concentrated to yield 25.3 g of crudeproduct. The crude product was dissolved in ether and stirred with 250ml of 5% copper (II) acetate. The resulting copper salt was filtered,washed with ether and stirred with 6N hydrochloric acid to destroy thesalt. The extract was washed with ether to yield 22.15 grams of thedesired product m.p. 138°-140° C. (77.7% yield). The structure wasconfirmed by instrumental analysis.

The compounds of Embodiment B of the present invention can be preparedby the following general method. ##STR34##

Generally, mole amounts of the dione and substituted benzoyl cyanide areused, along with a slight mole excess of zinc chloride. The tworeactants and the zinc chloride are combined in a solvent such asmethylene chloride. A slight mole excess of triethylamine is slowlyadded to the reaction mixture with cooling. The mixture is stirred atroom temperature for 5 hours.

The reaction product is worked up by conventional techniques.

The above-described substituted benzoyl cyanide can be preparedaccording to the teaching of T. S. Oakwood and C. A. Weisgerber, OrganicSynthesis Collected, Vol. III, pp. 122 (1955).

The following example teaches the synthesis of a representative compoundof Embodiment B of this invention.

EXAMPLE 1-B 4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione##STR35##

4,4-Dimethyl-1,3-cyclohexanedione [14.0 grams (g), 0.1 mole], 20.0 g(0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous,powdered zinc chloride were combined in 100 milliliters (ml) methylenechloride. Triethylamine (10.1 g, 0.12 mole) was slowly added withcooling. The reaction mixture was stirred at room temperature for 5hours and then poured into 2N hydrochloric acid. The aqueous phase wasdiscarded and the organic phase was washed with 150 ml 5% Na₂ CO₃ fourtimes. The aqueous washings were combined and acidified with HCl,extracted with methylene chloride, dried and concentrated to yield 25.3g of crude product. The crude product was chromatographed (2% AcOH/CH₂Cl₂) in 5 g aliquots then reduced on rotavap under reduced pressure at50° C. for 30 minutes to remove AcOH. This yielded an oil (40% yield).The structure was confirmed by instrumental analysis.

The compounds of Embodiment C of the present invention can be preparedby the following general method. ##STR36##

Generally, in step (1) mole amounts of the dione and substituted benzoylchloride are used, along with a slight mole excess of triethylamine. Thetwo reactants are combined in a solvent such as methylene chloride. Thetriethylamine is slowly added to the reaction mixture with cooling. Themixture is stirred at room temperature for several hours.

The reaction product is worked up by conventional techniques. ##STR37##

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the triethylamine, preferably 2 moles of thetriethylamine and up to 0.5 mole, preferably 0.1 mole of a cyanidesource (e.g., potassium cyanide or acetone cyanohydrin). The mixture isstirred in a reaction pot for about one hour at room temperature and thedesired product is recovered by conventional techniques.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR38## wherein R²⁷ and R²⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of the The Chemistry ofCarboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, NewYork, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D.F. Pearson, J. Wiley and Sons, (1970).

The following are two representative examples of the methods describedtherein. ##STR39## wherein R²⁷ and R²⁸ are as previously defined.

In reaction (a) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR40## wherein R²⁷ and R²⁸ are as previously defined.

In reaction (b) the substituted toluene is heated to reflux in anaqueous solution of potassium permanganate for several hours. Thesolution is then filtered and the reaction product is isolated byconventional techniques.

The following example teaches the synthesis of a representative compoundof Embodiment C of this invention.

EXAMPLE 1-C 2-(2'-Cyanobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione##STR41##

2-Cyanobenzoyl chloride (3.9 g, 24 mmol) and4,4-dimethyl-1,3-cyclohexanedione (3.3 g, 24 mmol) were dissolved in 75ml methylene chloride. Triethylamine (5.0 ml, 36 mmol) was addeddropwise and the resulting solution stirred for one and one-half hoursat room temperature. The solution was washed with water, 2 normalhydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K₂ CO₃)and saturated sodium chloride solution (brine), dried over anhydrousmagnesium sulfate (MgSO₄) and concentrated under vacuum. The residue wasdissolved in 20 ml acetonitrile. Triethylamine (4.4 ml, 32 mmol) andacetone cyanohydrin (5 drops) were added and the solution stirred fortwo hours. After dilution with ether, the solution was washed with 2NHCl and extracted with 5% K₂ CO₃. The aqueous extract was acidified withconcentrated hydrochloric acid and extracted with ether. The ether waswashed with water and brine, dried (MgSO₄) and concentrated undervacuum. The residue was purified by silica gel chromatography, yielding1.2 g of a viscous oil which was identified as the desired compound bynuclear magnetic resonance spectroscopy, infrared spectroscopy and massspectroscopy.

The compounds of Embodiments D and D' of the present invention can beprepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the ester, or in one step by inclusion of the cyanide source at thestart of reaction (1). ##STR42## wherein R³¹ through R³⁸ and moderatebase are as defined and X is halogen, preferably chlorine, C₁ -C₄alkyl-C(O)-O-, C₁ -C₄ alkoxy-C(O)-O- or ##STR43## wherein R³⁷ and R³⁸ inthis portion of the molecule are identical with those in the reactantshown above and the moderate base is as defined, preferably tri-C₁ -C₆alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoylreactant are used, along with a mole amount or excess of the base. Thetwo reactants are combined in an organic solvent such as methylenechloride, toluene, ethyl acetate or dimethylformamide. The base orbenzoyl reactant preferably are added to the reaction mixture withcooling. The mixture is stirred at 0° C.-50° C. until the reaction issubstantially complete. ##STR44## wherein the moderate base and R³¹through R³⁸ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the base, preferably about 2 moles of moderate baseand from 0.01 mole to about 0.5 mole or higher, preferably around 0.1mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 50° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases such astertiary amines and inorganic bases such as alkali metal carbonates andphosphates. Suitable tertiary amines include trialkylamines such astriethylamine. Suitable inorganic bases include potassium carbonate andtrisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the Crownethers.

A number of different solvents may be usable in this process, dependingon the nature of the acid chloride or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangement may be conducted at temperatures up to about50° C.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR45## wherein R³⁷ and R³⁸ are as previously defined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are three representative examples of the methods describedtherein. ##STR46## wherein R³⁷ and R³⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR47##wherein R³⁷ and R³⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR48## wherein R³⁷ and R³⁸ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in anaqueous solution of potassium permanganate for several hours. Thesolution is then filtered and the reaction product is isolated byconventional techniques.

The following examples teach the synthesis of representative compoundsof Embodiment D and D' of this invention.

EXAMPLE 1-D,D' 2-(2'-Nitrobenzoyl)-1,3-cyclohexanedione ##STR49##

2-Nitrobenzoyl chloride (5.0 g, 27 mmol) and cyclohexanedione (3.0 g, 27mmol) were dissolved in methylene chloride. Triethylamine (4.9 ml, 35mmol) was added dropwise and the resulting solution stirred for onehour. The solution was washed with 2 normal hydrochloric acid (2N HCl),water, 5% potassium carbonate solution and saturated sodium chloridesolution, dried over anhydrous magnesium sulfate (MgSO₄) andconcentrated under vacuum. The residue was dissolved in 20 mlacetonitrile. Triethylamine (1 equivalent) and potassium cyanide (40 mol%) were added and the solution stirred for one hour at room temperature.After dilution with ether, the solution was washed with 2N HCl andextracted with 5% potassium carbonate solution. The aqueous extract wasacidified and ether was added. Filtration of the resulting mixtureyielded 3.2 g of the desired compound (m.p. 132°-135° C.) which wasidentified by nuclear magnetic resonance spectroscopy, infraredspectroscopy and mass spectroscopy.

EXAMPLE 2-D,D' 2-(2'-Nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione##STR50##

Triethylamine (3.4 ml, 25 mmol) was added dropwise to a methylenechloride solution of 2-nitrobenzoyl chloride (3.5 g, 19 mmol) and5,5-dimethylcyclohexanedione (2.4 g, 19 mmol). After stirring for onehour at room temperature an additional 3 equivalents of triethylamineand 0.4 ml acetone cyanohydrin were added. The solution was stirred for2.5 hours, then washed with 2N HCl and extracted with 5% potassiumcarbonate solution. The basic extracts were acidified with 2N HCl andextracted with ether. The ether portion was washed with saturated sodiumchloride solution, dried over anhydrous magnesium sulfate andconcentrated under vacuum. The residue was recrytallized from ethylacetate yielding 2.0 g of the desired compound (m.p. 130°-133° C.) whichwas identified as such by nuclear magnetic resonance spectroscopy,infrared spectroscopy and mass spectroscopy.

The compounds of Embodiments E and E' of the present invention can beprepared by the following two or three step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR51## wherein moderate base, and R⁴⁰through R⁴⁸ are defined herein, and X is halogen, preferably chlorine,C₁ -C₄ alkyl-C(O)-O-, C₁ -C₄ alkoxy-C(O)-O- or ##STR52## wherein R⁴⁰,R⁴⁷ and R⁴⁸ in this portion of the moledule are identical with those inthe reactant shown above, and the moderate base is as defined,preferably tri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metalphosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoylreactant are used, along with a mole amount or excess of the base. Thetwo reactants are combined in an organic solvent such as methylenechloride, toluene, ethyl acetate or dimethylformamide. The base orbenzoyl reactant preferably are added to the reaction mixture withcooling. The mixture is stirred at 0° C.-50° C. until the reaction issubstantially complete. ##STR53##

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the base, preferably about 2 moles of moderate baseand from 0.01 mole to about 0.5 mole or higher, preferably around 0.1mole of the cyanide source (e.g., potassium cyanide oracetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 50° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases such astertiary amines and inorganic bases such as alkali metal carbonates andphosphates. Suitable tertiary amines include trialkylamines such astriethylamine. Suitable inorganic bases include potassium carbonate andtrisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the Crownethers.

A number of different solvents may be usable in this process, dependingon the nature of the acid chloride or the acylated product. A preferredsolvent for this reaction is 1, 2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangment may be conducted at temperatures up to about50° C. ##STR54## wherein n is 1 or 2.

Generally in step (3), a mole of the reaction product of step (2) isreacted with a slight mole or two mole excess of of an oxidizing agentsuch as m-chloroperbenzoic acid after being dissolved in a solvent suchas methylene chloride. After completion of the reaction, the resultingmixture is stripped under vacuum. The residue is purified by silica gelchromatography to yield the desired product.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR55## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previouslydefined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of the The Chemistry ofCarboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons NewYork, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D.F. Pearson, J. Wiley and Sons, (1970).

The following are three representative examples of the methods describedtherein. ##STR56## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR57##wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR58## wherein R⁴⁰, R⁴⁷ and R⁴⁸ are as defined and X is chlorine,bromine or iodine.

In reaction (c) the substituted aromatic halide is allowed to react withmagnesium in a solvent such as ether. The solution is then poured overcrushed dry ice and the benzoic acid is isolated by conventionaltechniques.

The following examples teach the synthesis representative compounds ofEmbodiments E and E' of this invention.

EXAMPLE 1-E,E'2-(2'-Methylthiobenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR59##

2-Methylthiobenzoyl chloride (7.2 g, 39 mmol) and4,4,6-trimethylcyclohexanedione (5.0 g, 39 mmol) were dissolved inmethylene chloride. Triethylamine (7.0 ml, 50 mmol) was added dropwiseand the resulting solution stirred for one hour at room temperature. Thesolution was washed with 2 normal hydrochloric acid (2N HCl), 5%potassium carbonate solution (5% K₂ CO₃) and saturated sodium chloridesolution (brine), dried over anhydrous magnesium sulfate (MgSO₄) andconcentrated under vacuum. The residue was dissolved in 20 mlacetonitrile. Triethylamine (2.5 equivalents) and acetone cyanohydrin(0.4 ml) were added and the solution stirred for 45 minutes at roomtemperature. After dilution with ether, the solution was washed with 2NHCl and extracted with 5% K₂ CO₃. The aqueous extract was acidified withhydrochloric acid and extracted with ether. The ether was washed withbrine, dried (MgSO₄) and concentrated under vacuum. The residue waspurified by trituration with ether, yielding 5.0 g of a viscous oilwhich was identified as the desired compound by nuclear magneticresonance spectroscopy (nmr), infrared spectroscopy (ir) and massspectroscopy (ms).

EXAMPLE 2-E,E' 2-(2'-Methanesulfonylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR60##

The benzoyl cyclohexanedione prepared in Example 1 (2.5 g, 7.9 mmol) wasdissolved in 40 ml methylene chloride. m-Chloroperbenzoic acid (3.5 g,16 mmol) was added and the resulting solution was stirred for 45minutes. The solution was concentrated under vacuum. Purification of theresidue by silica gel chromatography yielded 1.7 g of a viscous oilwhich was identified as the desired compound by nmr, ir and ms.

EXAMPLE 3-E,E'2-(4'-Trifluoromethyl-2'-methanesulfinylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione##STR61##

2-(4'-Trifluoromethyl-2'-methylthiobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione(5.0 g, 14 mmol) (which was prepared according to the method ofExample 1) was dissolved in 50 ml methylene chloride. A solution ofm-chloroperbenzoic acid (2.4 g--80%, 14 mmol) in 50 ml methylenechloride was added dropwise and the resulting solution was stirred forthree hours at room temperature. After concentration under vacuum, theresidue was dissolved in ether and washed with 1% hydrochloric acid. A5% copper (II) acetate solution was added to the ether fraction,followed by hexane. The liquid phase was decanted and the remaininggummy solid stirred with 6N HCl and ether. The ether layer was dried(MgSO₄) and concentrated to give 4.7 of a thick yellow solid.Purification on a centrifugally accelerated thin layer chromatograph (4mm silica gel, 50:50:1 hexane:ethyl acetate:acetic acid-eluent) yielded2.4 g of a viscous oil which was identified as the desired compound bynmr, ir and ms.

The compounds of Embodiments F and F' of the present invention can beprepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR62## wherein R⁵⁰ through R⁵⁸ are asdefined and X is halogen, preferably chlorine, C₁ -C₄ alkyl-C(O)-O-, C₁-C₄ alkoxy-C(O)-O- or ##STR63## wherein R⁵⁰, R⁵⁷ and R⁵⁸ in this portionof the molecule are identical with those in the reactant shown above andthe moderate base is as defined, preferably tri-C₁ -C₆ alkylamine,alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the dione and substituted benzoylreactant are used, along with a mole amount or excess of the base. Thetwo reactants are combined in an organic solvent such as methylenechloride, toluene, ethyl acetate or dimethylformamide. The base orbenzoyl reactant preferably are added to the reaction mixture withcooling. The mixture is stirred at 0° C.-50° C. until the reaction issubstantially complete.

The reaction product is worked up by conventional techniques. ##STR64##wherein R⁵⁰ through R⁵⁸ are as defined.

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the base, preferably about 2 moles of moderate baseand from 0.01 mole to about 0.5 mole or higher, preferably around 0.1mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 80° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reproducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases such astertiary amines and inorganic bases such as alkali metal carbonates andphosphates. Suitable tertiary amines include trialkylamines such astriethylamine. Suitable inorganic bases include potassium carbonate andtrisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the Crownethers.

A number of different solvents may be usable in this process, dependingon the nature of the acid chloride or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangment may be conducted at temperatures up to about50° C.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR65## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previouslydefined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are four representative examples of the methods describedtherein. ##STR66## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR67##wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR68## wherein R⁵⁰, R⁵⁷ and R⁵⁸ are as defined and X is chlorine,bromine or iodine.

The substituted aromatic halide is allowed to react with magnesium in asolvent such as ether. The solution is then poured over crushed dry iceand the benzoic acid is isolated by conventional techniques.

The following example teachs the synthesis of a representative compoundof Embodiments F and F' of this invention.

EXAMPLE 1-F,F'2-(4'-Bromo-2'-trifluoromethylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione##STR69##

4-Bromo-2-trifluoromethylbenzoyl chloride (4.3 g, 15 mmol) and4,4,6-trimethyl-1,3-cyclohexanedione (2.3 g, 15 mmol) were dissolved in100 ml methylene chloride. The solution was cooled with an ice bath andtriethylamine (2.1 ml, 15 mmol) in 10 ml methylene chloride was addeddropwise. The ice bath was then removed and the resulting solutionstirred for 30 minutes at room temperature. The solution was washed with2N hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K₂CO₃) and saturated sodium chloride solution (brine), dried overanhydrous magnesium sulfate (MgSO₄) and concentrated under vacuum. Theresidue (5.1 g) was dissolved in 20 ml acetonitrile. Triethylamine (3.5ml, 25 mmol) and 0.4 ml acetone cyanohydrin were added and the solutionstirred for two hours at room temperature while protected by a dryingtube (calcium sulfate). After dilution with ether, the solution waswashed with 2N HCl and extracted with 5 % K₂ CO₃. The aqueous extractwas acidified with concentrated hydrochloric acid and extracted withether. The ether was washed with brine, dried (MgSO₄) and concentratedunder vacuum. The resulting oil was purified on a silica gel column(80:20:1 hexane:ethyl acetate: acetic acid-eluent), yielding 1.5 g of aviscous oil which was identified as the desired compound by nuclearmagnetic resonance spectroscopy, infrared spectroscopy and massspectroscopy.

The compounds of Embodiment G and G' of the present invention can beprepared by the following two-step general method.

The process proceeds via the production of an enol ester intermediate asshown in reaction (1). The final product is obtained by rearrangement ofthe enol ester as shown in reaction (2). The two reactions may beconducted as separate steps by isolation and recovery of the enol esterusing conventional techniques prior to conducting step (2), or byaddition of a cyanide source to the reaction medium after the formationof the enol ester, or in one step by inclusion of the cyanide source atthe start of reaction (1). ##STR70## wherein R⁶⁰ through R⁶⁶ andmoderate base are as defined and X is halogen, preferably chlorine, C₁-C₄ alkyl-C(O)-O-, C₁ -C₄ alkoxy-C(O)-O- or ##STR71## wherein R⁶⁰, R⁶⁵and R⁶⁶ in this portion of the molecule are identical with those in thereactant shown above and the moderate base is as defined, preferablytri-C₁ -C₆ alkylamine, alkali metal carbonate or alkali metal phosphate.

Generally, in step (1) mole amounts of the trione and substitutedbenzoyl reactant are used, along with a mole amount or excess of thebase. The two reactants are combined in an organic solvent such asmethylene chloride, toluene, ethyl acetate or dimethylformamide. Thebase or benzoyl reactant preferably is added to the reaction mixturewith cooling. The mixture is stirred at 0° C.-50° C. until the reactionis substantially complete. ##STR72## wherein the moderate base and R⁶⁰through R⁶⁶ are as defined above.

Generally, in step (2) a mole of the enol ester intermediate is reactedwith 1 to 4 moles of the moderate base, preferably about 2 moles ofmoderate base and from 0.01 mole to about 0.5 mole or higher, preferablyabout 0.1 mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until therearrangement is substantially complete at a temperature below 50° C.,preferably about 20° C. to about 40° C., and the desired product isrecovered by conventional techniques.

The term "cyanide source" refers to a substance or substances whichunder the rearrangement conditions consists of or generates hydrogencyanide and/or cyanide anion.

The process is conducted in the presence of a catalytic amount of asource of cyanide anion and/or hydrogen cyanide, together with a molarexcess, with respect to the enol ester, of a moderate base.

Preferred cyanide sources are alkali metal cyanides such as sodium andpotassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4carbon atoms in the alkyl groups, such as acetone or methyl isobutylketone cyanohydrins; cyanohydrins of benzaldehyde or of C₂ -C₅ aliphaticaldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins;zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silylcyanide; and hydrogen cyanide itself. Hydrogen cyanide is consideredmost advantageous as it produces relatively rapid reaction and isinexpensive. Among cyanohydrins the preferred cyanide source is acetonecyanohydrin.

The cyanide source is used in an amount up to about 50 mole percentbased on the enol ester. It may be used in as little as about 1 molepercent to produce an acceptable rate of reaction at about 40° C. on asmall scale. Larger scale reactions give more reporducible results withslightly higher catalyst levels of about 2 mole percent. Generally about1-10 mole % of the cyanide source is preferred.

The process is conducted with a molar excess, with respect to the enolester, of a moderate base. By the term "moderate base" is meant asubstance which acts as a base yet whose strength or activity as a baselies between that of strong bases such as hydroxides (which could causehydrolysis of the enol ester) and that of weak bases such asbicarbonates (which would not function effectively). Moderate basessuitable for use in this embodiment include both organic bases, e.g.,trialkylamines such as triethylamine and inorganic bases such as alkalimetal carbonates and phosphates. Suitable inorganic bases includepotassium carbonate and trisodium phosphate.

The base is used in an amount of from about 1 to about 4 moles per moleof enol ester, preferably about 2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularlypotassium cyanide, a phase transfer catalyst may be included in thereaction. Particularly suitable phase transfer catalysts are the crownethers.

A number of different solvents are useful in this process, depending onthe nature of the acid halide or the acylated product. A preferredsolvent for this reaction is 1,2-dichloroethane. Other solvents whichmay be employed, depending on the reactants or products include toluene,acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, andmethyl isobutyl ketone (MIBK).

In general, depending on the nature of the reactants and the cyanidesource, the rearrangment may be conducted at temperatures up to about50° C.

The above described substituted benzoyl chlorides can be prepared fromthe corresponding substituted benzoic acids according to the teaching ofReagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp.767-769 (1967). ##STR73## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previouslydefined.

The substituted benzoic acids can be prepared by a wide variety ofgeneral methods according to the teaching of The Chemistry of CarboxylicAcids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N. Y.(1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson,J. Wiley and Sons, (1970).

The following are three representative examples of the methods describedtherein. ##STR74## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (a) the substituted benzonitrile is heated to reflux inaqueous sulfuric acid for several hours. The mixture is cooled and thereaction product is isolated by conventional techniques. ##STR75##wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (b) the substituted acetophenone is heated to reflux forseveral hours in an aqueous hypochlorite solution. The mixture is cooledand the reaction product is isolated by conventional techniques.##STR76## wherein R⁶⁰, R⁶⁵ and R⁶⁶ are as previously defined.

In reaction (c) the substituted toluene is heated to reflux in anaqueous solution of potassium permanganate for several hours. Thesolution is then filtered and the reaction product is isolated byconventional techniques.

The following example teaches the synthesis of a representative compoundof Embodiment G and G' of this invention.

EXAMPLE 1-G,G'2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione##STR77##

2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) weredissolved in methylene chloride. Triethylamine was added and theresulting solution stirred at room temperature for 30 minutes. Thesolution was washed with 1 normal hydrochloric acid (1N HCl), andsaturated sodium chloride (brine), dried over anhydrous magnesiumsulfate (MgSO₄) and concentrated under vacuum. The residue was dissolvedin 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetonecyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirredat room temperature for 4 hours. After dilution with ether, the solutionwas washed with 1N HCl and extracted with 5% K₂ CO₃. The basic extractwas acidified with HCl and extracted with ether. The ether extract waswashed with brine, dried over MgSO₄ and concentrated under vacuum,yielding 2.2 g of crude product. This was recrystallized from benzene toremove syncarpic acid still present. Concentration of the mother liquorunder vacuum gave 1.7 g of the desired product as an oil, whichsolidified on standing (m.p. 76°-82° C.). It was identified as such bynuclear magnetic resonance spectroscopy, infrared spectroscopy and massspectroscopy.

The following are tables of certain selected compounds of EmbodimentsA-G' that are preparable according to the procedures described herein.Compound numbers are assigned to each compound and are used throughoutthe remainder of the application.

                                      TABLE I-A                                   __________________________________________________________________________     ##STR78##                                                                    Cmpd.                                         n.sub.D.sup.30 or               No. R         R.sup.1                                                                          R.sup.2                                                                           R.sup.3    R.sup.4  R.sup.5                                                                            m.p. °C.                 __________________________________________________________________________    1A  CH.sub.3  CH.sub.3                                                                         Cl  H          H        H    1.5613                          2A  CH.sub.3  CH.sub.3                                                                         Cl  H          4-Cl     H    1.5655                          3A  CH.sub.3  CH.sub.3                                                                         Cl  H          H        6-Cl 103-108                         4A* H         H  Cl  H          4-Cl     H    138-140                         5A  CH.sub.3  CH.sub.3                                                                         Br  H          H        H                                    6A  CH.sub.3  CH.sub.3                                                                         Cl  H          H        5-Cl 74-77                           7A  H         H  Cl  H          H        5-Cl 104-107                         8A  H         H  Br  H          H        H    93-96                           9A  H         H  Cl  H          H        H    79-87                           10A H         H  I   H          H        H    66-70                           11A H         H  Cl  H          4-NO.sub.2                                                                             H    118-122                         12A H         H  Cl  H          H        6-Cl 143-148                         13A H         H  Cl  H          H        5-Br 109-115                         14A H         H  I   3-I        H        5-I  164-167                         15A H         H  Cl  H          H        5-CH.sub.3                                                                         60-65                           16A H         H  Cl  H          4-CH.sub.3                                                                             H    79-86                           17A H         H  Cl  H          4-CH.sub.3 O                                                                           H    60-63                           18A H         H  Cl  3-Cl       H        6-Cl                                 19A H         H  Cl  H          H        5-CH.sub.3 O                                                                       77-80                           20A H         H  Cl  3-Cl       H        H    80-90                           21A H         H  Cl  H          H        5-CF.sub.3                                                                         74-75                           22A H         H  Cl  H          H        5-NO.sub.2                                                                         140-143                         23A H         H  Cl  3-Cl       4-Cl     H    152-154                         24A H         H  Cl  3-Cl       4-CH.sub.3 O                                                                           H    169-170                         25A H         H  Cl  H          4-Br     H    104-107                         26A CH.sub.3  CH.sub.3                                                                         CH.sub.3 O                                                                        H          H        H    104-108                         27A H         H  Cl  H                                                                                         ##STR79##                                                                             H                                    28A H         H  Br  H          H        (a)                                  29A H         H  CH.sub.3 O                                                                        3-CH.sub.3 O                                                                             H        H    75-79                           30A H         H  CH.sub.3 O                                                                        H          H        5-CH.sub.3 O                                                                       89-92                           31A H         H  Br  H          4-CH.sub.3 O                                                                           5-CH.sub.3 O                                                                       92-96                           32A H         H  Br  H           (4)-OCH.sub.2 O-(5)                                                                        63-68                           33A CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-Cl     H    86-89                           34A H         H  Cl  3-Cl       H        5-Cl                                 35A CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       H        5-Cl 105-109                         36A CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-Cl     5-Cl 137-139                         37A H         H  Cl  3-Cl       4-Cl     5-Cl 106-110                         38A H         H  Cl  H          4-Cl     5-Cl 108-111                         39A                                                                                ##STR80##                                                                              H  Cl  H          4-Cl     H                                    40A                                                                                ##STR81##                                                                              H  Cl  H          4-Cl     H                                    41A CH(CH.sub.3).sub.2                                                                      H  Cl  H          4-Cl     H                                    42A CH(CH.sub.3).sub.2                                                                      H  Cl  3-Cl       4-Cl     H                                    43A H         H  Cl  H          4-F      H                                    44A sodium salt of Compound No. 23            85-94                           45A isopropylamine salt of Compound No. 23    160-165                         46A triethylamine salt of Compound No. 23     82-85                           47A potassium salt of Compound No. 23         107-106                         48A triethanolammonium salt of Compound No. 39                                49A sodium salt of Compound No. 43            60-63                           50A CH(CH.sub.3).sub.2                                                                      H  Cl  3-CH.sub.3 O                                                                             4-Br     H                                    51A H         H  Cl  H          4-CH.sub.3 SO.sub.2                                                                    H    140-141                         52A H         CH.sub.3                                                                         Cl  H          4-Cl     H                                    53A i-C.sub.4 H.sub.9                                                                       H  Cl  H          4-Cl     H                                    54A i-C.sub.3 H.sub.7                                                                       H  Cl  3-CH.sub.3 O                                                                             H        H                                    55A CH.sub.3  CH.sub.3                                                                         Cl  H          4-CH.sub.3 SO.sub.2                                                                    H                                    56A CH.sub.3  CH.sub.3                                                                         Cl  3-CH.sub.3 4-Cl     H                                    57A H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                           58A H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H     98-102                         59A H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.2                                                             H     98-109                         60A H         H  Cl  H          4-C.sub.3 H.sub.7 SO.sub.2                                                             H    semi-solid                      61A H         H  Cl  3-CH.sub.3 O                                                                             4-CH.sub.3 SO.sub.2                                                                    H    48-59                           62A CH.sub.3  CH.sub.3                                                                         Cl  H          4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    semi-solid                      63A H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H      145-148.5                     64A H         H  Cl  3-C.sub.2 H.sub.5 S                                                                      4-C.sub.2 H.sub.5 SO.sub.2                                                             H    oil                             65A CH.sub.3  CH.sub.3                                                                         Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H    103-108                         66A CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-C.sub.2 H.sub.5 SO.sub.2                                                             H    108-114                         67A i-C.sub.3 H.sub.7                                                                       H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H    brown gum                       68A H         H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                                                                    H    145-154                         69A i-C.sub.3 H.sub.7                                                                       H  Cl  3-Cl       4-CH.sub.3 SO.sub.2                                                                    H                                    70A H         H  Br  H          4-CH.sub.3 SO.sub.2                                                                    H    brown gum                       71A H         H  Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2                                                           H    semi-solid                      72A H         H  Cl  H          4-CH.sub.3 S                                                                           H    74-77                           73A H         H  Cl  3-Cl       4-CH.sub.3 S                                                                           H                                    74A CH.sub.3  CH.sub.3                                                                         Cl  3-Cl       4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    120-123                         75A H         H  Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2                                                           H    semi-solid                      76A CH.sub.3  CH.sub.3                                                                         Cl  H          4-n-C.sub.4 H.sub.9 SO.sub.2                                                           H                                    77A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-CH.sub.3 SO.sub.2                                                                    H    semi-solid                      78A H         H  Cl  3-CH.sub.3 O                                                                             4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    golden gum                      79A CH.sub.3  CH.sub.3                                                                         Cl  H          4-i-C.sub.3 H.sub.7 SO.sub.2                                                           H    125-128                         80A CH(CH.sub.3).sub.2                                                                      H  CH.sub.3 O                                                                        3-Cl       5-Cl     H                                    81A H         H  Cl  3-CH.sub.3 O                                                                             4-Br     H    110-111                         82A H         H  Cl  3-CH.sub.3 4-Cl     H    56-64                           83A H         H  Cl  H          4-Cl     5-CH.sub.3 O                                                                       softens >70                     84A CH(CH.sub.3).sub.2                                                                      H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-Br     H                                    85A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-Br     H    101-104                         86A H         H  Cl  H          4-i-C.sub.4 H.sub.9 SO.sub.2                                                           H    136-140                         87A CH.sub.3  CH.sub.3                                                                         Cl  H          4-i-C.sub.4 H.sub.9 SO.sub.2                                                           H                                    88A H         H  Cl  3-Cl       4-i-C.sub.3 H.sub.7 SO.sub.2                                                           H    173-176                         89A H         H  Cl  3-Cl       4-n-C.sub.4 H.sub.9 SO.sub.2                                                           H    135-138                         90A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-C.sub.2 H.sub.5 SO.sub.2                                                             H    gum                             91A H         H  Cl  3-CH.sub.3 O                                                                             4-C.sub.2 H.sub.5 SO.sub.2                                                             H    gum                             92A H         H  Cl  3-Cl       4-C.sub.2 H.sub.5 S                                                                    H    91-94                           93A H         H  Cl  3-C.sub.2 H.sub.5 S                                                                      4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H    oil                             94A H         H  Cl  3-C.sub.2 H.sub.5 S                                                                      4-C.sub.2 H.sub.5 S                                                                    H    oil                             95A H         H  Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2                                                           H    oil                             96A H         H  Cl  3-C.sub.2 H.sub.5 O                                                                      4-n-C.sub.3 H.sub.7 SO.sub.2                                                           H                                    97A H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H    oil                             98A CH.sub.3  CH.sub.3                                                                         Cl  H          4-(CH.sub.3).sub.2 NSO.sub.2                                                           H    oil                             99A H         H  Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                    H    90-92                           100A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                    H                                    101A                                                                              H         H  Cl  H          4-C.sub.2 H.sub.5 S                                                                    H                                    102A                                                                              H         H  Cl  H          4-n-C.sub.3 H.sub.7 S                                                                  H                                    103A                                                                              H         H  Cl  H          4-i-C.sub.3 H.sub.7 S                                                                  H                                    104A                                                                              H         H  Cl  H          4-C.sub.2 H.sub.5 SO                                                                   H                                    105A                                                                              H         H  CH.sub.3 O                                                                        H          4-NO.sub.2                                                                             H    semi-solid                      106A                                                                              H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-Br     H                                    107A                                                                              H         H  Cl  3-n-C.sub.3 H.sub.7 O                                                                    4-CH.sub.3 SO.sub.2                                                                    H     96-100                         108A                                                                              H         H  Cl  3-allyloxy 4-CH.sub.3 SO.sub.2                                                                    H    semi-solid                      109A                                                                              H         H  Cl  3-CH.sub.3 C(O)NH                                                                        4-Cl     H    155-160                         110A                                                                              H         H  Cl  3-Cl       4-n-C.sub.3 H.sub.7 S                                                                  H                                    111A                                                                              H         H  Cl  3-CH.sub.3 O                                                                             4-NO.sub.2                                                                             H    150-153                         112A                                                                              H         H  Cl  3-allyloxy 4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    113A                                                                              H         H  Cl  3-CH.sub.2 BrCHBrCH.sub.2 O                                                              4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    114A                                                                              H         H  Cl  3-n-C.sub.4 H.sub.9 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H    gum                             115A                                                                              H         H  Cl  3-i-C.sub.4 H.sub.9 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    116A                                                                              H         H  Cl  H          4-allylthio                                                                            H                                    117A                                                                              CH.sub.3  CH.sub.3                                                                         Cl  H          4-NO.sub.2                                                                             H                                    118A                                                                              H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                                                               4-Cl     H                                    119A                                                                              H         H  Cl  3-i-C.sub.3 H.sub.7 O                                                                    4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    120A                                                                              H         H  Cl  3-CH.sub.2 ClCH.sub.2 CH.sub.2 O                                                         4-C.sub.2 H.sub.5 SO.sub.                                                              H    gum                             121A                                                                              H         H  Cl  H          4-t-C.sub.4 H.sub.9 S                                                                  H                                    122A                                                                              H         H  Cl  3-CH.sub.3 O                                                                             4-C.sub.2 H.sub.5 S                                                                    H                                    123A                                                                              H         H  Cl  H          4-CF.sub.3                                                                             H                                    124A                                                                              H         H  Cl  H          4-Cl     6-Cl                                 125A                                                                              H         H  Cl  3-CH.sub.3 C(O)N(CH.sub.3)                                                               H        H    131-135                         126A                                                                              H         H  Cl  3-CH.sub.3 C(O)NH                                                                        H        H                                    127A                                                                              H         H  Cl  3-(CH.sub.3).sub.2 N                                                                     4-Cl     H                                    128A                                                                              CH.sub.3  H  Cl  3-CH.sub.3 O                                                                             4-CH.sub.3 SO.sub.2                                                                    H    117-122                         129A                                                                              H         H  Cl  H          4-C.sub.2 H.sub.5 SO.sub.2                                                             H                                    130A                                                                              H         H  Br  H          H        H                                    131A                                                                              H         H  Br  H          4-C.sub.2 H.sub.5 OC(O)                                                                H                                    132A                                                                              H         H  Cl  H          4-CN     H    183-184                         133A                                                                              H         H  Cl  3-CH.sub.3 C(O)NH                                                                        H        6-NO.sub.2                           134A                                                                              H         H  Cl  3-(CH.sub.3).sub.2 N                                                                     H        H                                    135A                                                                              H         H  Cl  3-Cl       4-ClCH.sub.2 CH.sub.2 SO.sub.2                                                         H                                    __________________________________________________________________________     *Prepared in Example 1A.                                                      ##STR82##                                                                

                                      TABLE I-B                                   __________________________________________________________________________     ##STR83##                                                                    Compound                                                                      Number                                                                              R.sup.10 R.sup.11                                                                          R.sup.12                                                                          R.sup.13                                                                            R.sup.14  R.sup.15                                                                         R.sup.16                                                                         R.sup.17                                                                         R.sup.18                      __________________________________________________________________________     1B                                                                                  ##STR84##                                                                             H   Cl  H     4-Cl      H  H  H  H                              2B                                                                                  ##STR85##                                                                             CH.sub.3                                                                          Cl  H     4-Cl      H  H  H  H                              3B   triethanolammonium salt of Compound No. 2                                4B   triethanolammonium salt of Compound No. 7                                5B                                                                                  ##STR86##                                                                             CH.sub.3                                                                          Cl  3-Cl  4-Cl      H  H  H  H                              6B   triethanolammonium salt of Compound No. 5                               .sup. CH.sub.3a)                                                                             CH.sub.3                                                                          Cl  H     4-Cl      H  H  H  H                              8B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                              9B   CH.sub.3 n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl      H  H  H  H                             10B   CH.sub.3 H   Cl  H     4-Cl      H  H  H  H                             11B   CH.sub.3 H   Cl  H     4-Cl      CH.sub.3                                                                         H  H  H                             12B   C.sub.5 H.sub.10                                                                           Cl  H     4-Cl      H  H  H  H                             13B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-Cl      H  H  H  H                             14B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-Cl      CH.sub.3                                                                         H  H  H                             15B   i-C.sub.3 H.sub.7                                                                      H   Cl  3-Cl  4-Cl      H  H  H  H                             16B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             17B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 SO.sub.2                                                                     CH.sub.3                                                                         H  H  H                             18B   CH.sub.3 H   Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             19B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             20B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             21B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             22B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             23B   CH.sub.3 CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             24B   CH.sub.3 CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             25B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-Cl      H  H  H  H                             26B   CH.sub.3 CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-Cl      H  H  H  H                             27B   CH.sub.3 C.sub.2 H.sub.5                                                                   Cl  H     4-Cl      H  H  H  H                             28B   CH.sub.3 CH.sub.3                                                                          Cl  H     H         H  H  H  H                             29B   CH.sub. 3                                                                              CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-Br      H  H  H  H                             30B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Br      H  H  H  H                             31B   CH.sub.3 C.sub.2 H.sub.5                                                                   Cl  3-Cl  4-Cl      H  H  H  H                             32B   n-C.sub.3 H.sub.7                                                                      H   Cl  H     4-Cl      H  H  H  H                             33B                                                                                  ##STR87##                                                                             n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl      H  H  H  H                             34B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             35B   CH.sub.3 CH.sub.3                                                                          Cl  3-i-C.sub.3 H.sub.7 O                                                               4-Br      H  H  H  H                             36B   CH.sub.3 CH.sub.3                                                                          Cl  H     6-F       H  H  H  H                             37B   i-C.sub.3 H.sub.7                                                                      H   Cl  3-Cl  4-Cl      H  H  H  H                             38B   CH.sub.3 CH.sub.3                                                                          Cl  3-OC.sub.2 H.sub.5                                                                  4-Br      CH.sub.3                                                                         H  H  H                             39B   i-C.sub.3 H.sub.7 OC(O)                                                                H   Cl  H     4-Cl      H  H  H  H                             40B   C.sub.2 H.sub.5 OC(O)                                                                  n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl      H  H  H  H                             41B   C.sub.5 H.sub.10                                                                           Cl  H     4-Cl      H  H  H  H                             42B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Cl      H  H  CH.sub.3                                                                         H                             43B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             44B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             45B   CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        3-CH.sub.3 O                                                                        H         H  H  H  H                             46B   CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     4-Cl      H  H  H  H                             47B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-Br      CH.sub.3                                                                         H  H  H                             48B   CH.sub.3 CH.sub.3                                                                          Br  H     H         H  H  H  H                             49B   CH.sub.3 CH.sub.3                                                                          I   H     H         H  H  H  H                             50B   CH.sub.3 CH.sub.3                                                                          F   H     H         H  H  H  H                             51B   CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     H         H  H  H  H                             52B   CH.sub.3 CH.sub.3                                                                          Cl  3-allyloxy                                                                          4-Br      H  H  H  H                             53B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 SO.sub.2                                                                     H  H  CH.sub.3                                                                         H                             54B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        4-Br      CH.sub.3                                                                         H  H  H                             55B   CH.sub.3 CH.sub.3                                                                          Br  H     4-CN      H  H  H  H                             56B   CH.sub.3 CH.sub.3                                                                          Cl  H     4N(CH.sub.3)SO.sub.2 CF.sub.3                                                           H  H  H  H                             57B   CH.sub.3 CH.sub.3                                                                          Cl  3-NO.sub.2                                                                          H         H  H  H  H                             58B   CH.sub.3 CH.sub.3                                                                          C.sub.2 H.sub.5 O                                                                 H     4-Cl      H  H  H  H                             59B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             60B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             61B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             62B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             63B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                                                            CH.sub.3                                                                         H  H  H                             64B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                              CH.sub.3                                                                         H  H  H                             65B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-F       H  H  H  H                             66B   CH.sub.3 H   Cl  3-CH.sub.3 O                                                                        4-Br      H  H  H  H                             67B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        H         H  H  H  H                             68B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             69B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             70B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             71B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 S                                                                 4-CH.sub.3 SO.sub.2                                                                     H  H  H  H                             72B   CH.sub.3 CH.sub.3                                                                          Cl  Cl    4-i-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             73B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             74B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             75B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-Br      H  H  H  H                             76B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             77B   CH.sub.3 CH.sub.3                                                                          Cl  3-n-C.sub.3 H.sub.7 O                                                               4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             78B   CH.sub.3 CH.sub. 3                                                                         Cl  H     4-(CH.sub.3).sub.2 NSO.sub.2                                                            H  H  H  H                             79B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 S                                                                        4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             80B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             81B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             82B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2                                                     H  H  H  H                             83B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                            H  H  H  H                             84B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 S                                                                   CH.sub.3                                                                         H  H  H                             85B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 S(O)                                                                  H  H  H  H                             86B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.3 H.sub.7 S                                                                   H  H  H  H                             87B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-n-C.sub.3 H.sub.7 S                                                                   H  H  H  H                             88B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-t-C.sub.4 H.sub.9 SO.sub.2                                                            H  H  H  H                             89B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-i-C.sub.3 H.sub.7 S                                                                   CH.sub.3                                                                         H  H  H                             90B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO.sub.2                                                            CH.sub.3                                                                         H  H  H                             91B   CH.sub.3 CH.sub.3                                                                          Cl  *     4-Cl      H  H  H  H                             92B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.2CHCH.sub.2 S                                                                  H  H  H  H                             93B   CH.sub.3 CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             94B   CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-CH.sub.3 S                                                                            CH.sub.3                                                                         H  H  H                             95B   CH.sub.3 CH.sub.3                                                                          Cl  H     4-CH.sub.3 S                                                                            H  H  H  H                             96B   CH.sub.3 CH.sub.3                                                                          Cl  3-i-C.sub.3 H.sub.7 O                                                               4-C.sub.2 H.sub.5 SO.sub.2                                                              H  H  H  H                             97B   CH.sub.3 CH.sub.3                                                                          Cl  3-CH.sub.3 O                                                                        4-C.sub.2 H.sub.5 S                                                                     H  H  H  H                             98B   CH.sub.3 CH.sub.3                                                                          Cl  **    4-Cl      H  H  H  H                             99B   CH.sub.3 CH.sub.3                                                                          Cl  **    H         H  H  H  H                             100B  CH.sub.3 CH.sub.3                                                                          Cl  3-Cl  4-CH.sub.3 S                                                                            H  H  H  H                             101B  CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     4-NO.sub.2                                                                              H  H  H  H                             102B  CH.sub.3 CH.sub.3                                                                          CH.sub.3 O                                                                        H     4-CF.sub. 3                                                                             H  H  H  H                             103B  CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO                                                                  H  H  H  H                             104B  CH.sub.3 CH.sub.3                                                                          Cl  H     4-n-C.sub.3 H.sub.7 SO                                                                  CH.sub.3                                                                         H  H  H                             __________________________________________________________________________     .sup.a) Prepared in Example IB.                                               *3-CH.sub.3 C(O)NH                                                            **3-CH.sub.3 C(O)N(CH.sub.3)                                             

The following additional compounds can be prepared by the general methodhereinbefore taught.

                                      TABLE I-B                                   __________________________________________________________________________     ##STR88##                                                                    R.sup.10                                                                          R.sup.11                                                                          R.sup.12                                                                          R.sup.13                                                                            R.sup.14                                                                             R.sup.15                                                                         R.sup.16                                                                          R.sup.17                                                                         R.sup.18                                   __________________________________________________________________________    CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  H     4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  H     4-Cl   H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  H     4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  H     4-Cl   H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  H     4-Cl   CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  H     4-Cl   H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  H     4-Cl   CH.sub.3                                                                         H   H  H                                          i-C.sub. 3 H.sub.7                                                                H   Cl  H     4-Cl   H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  H     4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  H     4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-Cl   H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-Cl   H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-Cl  4-Cl   H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-Cl  4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-Cl  4-Cl   H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-Cl  4-Cl   CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-Cl  4-Cl   H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-Cl  4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-Cl  4-Cl   H  H   H   H                                         C.sub.5 H.sub.10                                                                      Cl  3-Cl  4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  H     4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  H     4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  H     4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  H     4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  H     4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  H     4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  H     4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  H     4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub. 5 H.sub.10                                                                     Cl  H     4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  H     4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-Cl  4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub. 2                                                          H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-Cl  4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-OCH.sub.3                                                                         4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-CH.sub.3                                                                          4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-OCH.sub.3                                                                         4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                     H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-CH.sub.3                                                                          4-CH.sub.3 SO.sub.2                                                                  CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-Cl   H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-Cl   H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-CH.sub.3                                                                          4-Cl   H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-CH.sub.3                                                                          4-Cl   H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-CH.sub.3                                                                          4-Cl   H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-CH.sub.3                                                                          4-Cl   H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-CH.sub.3                                                                          4-Cl   H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-CH.sub.3                                                                          4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H   H                                         CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-Cl   H  H   H  H                                          CH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                 Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-Cl   H  H   H  H                                          CH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                 Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          H   Cl  3-OCH.sub.3                                                                         4-Cl   H  H   H  H                                          CH.sub.3                                                                          H   Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-OCH.sub.3                                                                         4-Cl   H  H   H  H                                          C.sub.2 H.sub.5                                                                   H   Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-OCH.sub.3                                                                         4-Cl   H  H   H  H                                          n-C.sub.4 H.sub.9                                                                 H   Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-OCH.sub.3                                                                         4-Cl   H  H   H  H                                          i-C.sub.3 H.sub.7                                                                 H   Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-OCH.sub.3                                                                         4-Cl   H  H   H  H                                          C.sub.5 H.sub.10                                                                      Cl  3-OCH.sub.3                                                                         4-Cl   CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-n-C.sub.3 H.sub.7 O                                                               4-Br   H  H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  H     4-C.sub.2 H.sub.5 SO.sub.2                                                           CH.sub.3                                                                         H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  H     4-NO.sub.2                                                                           H  H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-C.sub.2 H.sub.5 O                                                                 4-CH.sub.3 S                                                                         H  H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  H     4-CN   H  H   H  H                                          CH.sub.3                                                                          CH.sub.3                                                                          Cl  3-(CH.sub.3).sub.2 N                                                                4-Cl   H  H   H  H                                          __________________________________________________________________________

                                      TABLE I-C                                   __________________________________________________________________________     ##STR89##                                                                    Comp. No.                                                                           R.sup.21                                                                         R.sup.22                                                                         R.sup.23                                                                          R.sup.24                                                                         R.sup.25                                                                         R.sup.26                                                                         R.sup.27                                                                          R.sup.28                                                                         n.sub.D.sup.30 or m.p.                        __________________________________________________________________________    .sup. 1C.sup.a                                                                      CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   H  oil                                           2C    H  H  H   H  H  H  H   CN 124-140° C.                            __________________________________________________________________________     .sup.a Prepared in Example IC.                                           

                                      TABLE I-D                                   __________________________________________________________________________     ##STR90##                                                                    Comp.                                                                         No. R.sup.31                                                                         R.sup.32                                                                          R.sup.33                                                                          R.sup.34                                                                         R.sup.35                                                                         R.sup.36                                                                         R.sup.37                                                                           R.sup.38 n.sub.D.sup.30 or                       __________________________________________________________________________                                          m.p.                                     1D CH.sub.3                                                                         H   H   H  H  H  H    H        viscous oil                              2D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    H        viscous oil                              3D.sup.a)                                                                        H  H   H   H  H  H  H    H        132-135                                  4D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    H        viscous oil                              5D.sup.b)                                                                        H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    H        130-133                                  6D CH.sub.3                                                                         H   H   H  CH.sub.3                                                                         H  H    H        viscous oil                              7D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    CF.sub.3 52-61                                    8D H  H   H   H  H  H  H    CF.sub.3 88-94                                    9D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    CF.sub.3 89-97                                   10D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-CH.sub.3                                                                         H        119-122                                 11D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-Cl H        72-79                                   12D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    Cl       118-121                                 13D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-Cl H        118-120                                 14D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-F  H        130-133                                 15D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-CH.sub.3 O                                                                       H        139-142                                 16D CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                          H  H  H  H    CF.sub.3 viscous oil                             17D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    NO.sub.2 viscous oil                             18D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    Br       viscous oil                             19D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  CH.sub.3                                                                         5-CH.sub.3                                                                         H        viscous oil                             20D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-CH.sub.3                                                                         H        viscous oil                             21D H  H   H   H  H  H  H    F        123-128                                 22D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    F        viscous oil                             23D H  H   H   H  H  H  H    Cl       viscous oil                             24D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 CH.sub.3                                                                      130-133                                 25D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                                                            viscous oil                             26D H  H   H   H  H  H  H    SO.sub.2 CH.sub.3                                                                      157-159                                 27D H  H   H   H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                                                            120-123                                 28D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-F  H        165-195                                 29D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                                                                oil                                     30D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    SO.sub.2CH.sub.3                                                                       gum                                     31D CH.sub.3                                                                         n-C.sub.4 H.sub.9                                                                 H   H  H  H  H    H        viscous oil                             32D H  H   i-C.sub.4 H.sub.9                                                                 H  H  H  H    H        viscous oil                             33D H  H   H   H  H  H  H    SO.sub.2C.sub.2 H.sub.5                                                                viscous oil                             34D H  H   H   H  H  H  H    CN       viscous oil                             35D H  H   H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                                                             158-159                                 36D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 N(CH.sub.3).sub.2                                                             120-130                                 37D H  H   H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                      158-163                                 38D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                      oil                                     39D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H                                                                                   ##STR91##                                                                             oil                                     40D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    SO.sub.2N(C.sub.2 H.sub.5).sub.2                                                       oil                                     41D H  H   H   H  H  H  H    SC.sub.2 H.sub.5                                                                       oil                                     42D H  H   H   H  H  H  H    S(O)-n-C.sub.3 H.sub.7                                                                 oil                                     43D H  H   H   H  H  H  H    S-n-C.sub.3 H.sub.7                                                                    oil                                     44D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    S-n-C.sub.3 H.sub.7                                                                    oil                                     45D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    S-n-C.sub.3 H.sub.7                                                                    oil                                     46D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    SC.sub.2 H.sub.5                                                                       oil                                     47D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SC.sub.2 H.sub.5                                                                       oil                                     48D H  H   H   H  H  H  H    SCH.sub.3                                                                              94-97                                   49D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    CF.sub.3 oil                                     50D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SCH.sub.3                                                                              oil                                     51D c) H   i-C.sub.3 H.sub.7                                                                 H  H  H  H    H        145-148                                 52D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  5-CH.sub.3 O                                                                       Br       oil                                     53D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    Cl       oil                                     54D H  H   H   H  H  H  3-CH.sub.3 O                                                                       Cl       oil                                     55D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  3-CH.sub.3 O                                                                       Cl       oil                                     56D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    CH.sub.3 S                                                                             oil                                     57D H  H   H   H  H  H  H                                                                                   ##STR92##                                                                             120-125                                 58D H  H   CH.sub.3                                                                          CH.sub.3                                                                         H  H  H    CN       175-177                                 59D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    CN       151-153                                 60D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  H    CN       oil                                     61D c) H   H   H  H  H  H    H        oil                                     62D d) H   H   H  H  H  H    H        oil                                     63D H  H   CH.sub.3                                                                          H  H  H  H    Cl       110-115                                 64D H  H   CH.sub.3                                                                          H  H  H  H    SO.sub.2 -n-C.sub.3 H.sub.7                                                            oil                                     65D d) CH.sub.3                                                                          H   H  H  H  H    Cl       oil                                     66D H  H   H   H  H  H  H    SO.sub.2 CHCl.sub.2                                                                    oil                                     67D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 CHCl.sub.2                                                                    oil                                     68D H  H   H   H  H  H  c)   Br       oil                                     69D H  H   H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                                                                   oil                                     70D CH.sub.3                                                                         CH.sub.3                                                                          H   H  H  H  H    SO.sub.2 CH.sub.2 Cl                                                                   wax                                     71D d) CH.sub.3                                                                          H   H  H  H  H    H        oil                                     72D H  H   H   H  H  H  C.sub.2 H.sub.5 O                                                                  Cl       oil                                     73D CH.sub.3                                                                         CH.sub.3                                                                          H   H  CH.sub.3                                                                         H  CH.sub.3 O                                                                         CF.sub.3 oil                                     __________________________________________________________________________     .sup.a) Prepared in Example 1D,D'.                                            .sup.b) Prepared in Example 2D,D'.                                             c) = C.sub. 2 H.sub.5 OC(O)-                                                  d) = iC.sub.3 H.sub.7 OC(O)-                                            

                                      TABLE I-E                                   __________________________________________________________________________     ##STR93##                                                                    Comp.                                                                         No. n R.sup.40                                                                         R.sup.41                                                                         R.sup.42                                                                         R.sup.43                                                                         R.sup.44                                                                         R.sup.45                                                                         R.sup.46                                                                         R.sup.47                                                                          R.sup.48                                                                             m.p.                                    __________________________________________________________________________     1E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   H      79-81° C.                         2E 0 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   H      oil                                     .sup.  3E.sup.a)                                                                  0 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  CH.sub.3                                                                         H  H   H      oil                                     .sup.  4E.sup.b)                                                                  2 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  CH.sub.3                                                                         H  H   H      oil                                      5E 0 C.sub.2 H.sub.5                                                                  CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   H      oil                                      6E 2 C.sub.2 H.sub.5                                                                  CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   H      oil                                      7E 0 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              Cl     59-64° C.                         8E 2 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              Cl     116-119° C.                       9E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   CF.sub.3                                                                             102-106° C.                      10E 2 CH.sub.3                                                                         H  H  H  H  H  H  H   CF.sub.3                                                                             oil                                     11E 0 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   CF.sub.3                                                                             49-53° C.                        12E 2 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   CF.sub.3                                                                             oil                                       13E.sup.c)                                                                      1 CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H  H  H  H  H   CF.sub.3                                                                             oil                                     14E 0 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              SCH.sub.3                                                                            105-107° C.                      15E 1 CH.sub.3                                                                         H  H  H  H  H  H  3-Cl                                                                              S(O)CH.sub.3                                                                         oil                                     16E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                                                           oil                                     17E 0 CH.sub.3                                                                         H  H  H  H  H  H  H   SCH.sub.3                                                                            101-103° C.                      18E 2 CH.sub.3                                                                         H  H  H  H  H  H  H   SO.sub.2 n-C.sub.3 H.sub.7                                                           oil                                     19E 2 CH.sub.3                                                                         H  H  H  H  H  H  H   SO.sub.2 CH.sub.3                                                                    194-196° C.                      20E 0 CH.sub.3                                                                         H  H  H  H  H  H  3-CH.sub.3                                                                        H      40-42° C.                        21E 2 CH.sub.3                                                                         H  H  H  H  H  H  3-CH.sub.3                                                                        H      80-86° C.                        __________________________________________________________________________     .sup.a) Prepared in Example 1E,E'.                                            .sup.b) Prepared in Example 2E,E'.                                            .sup.c) Prepared in Example 3E,E'.                                       

                                      TABLE I-F                                   __________________________________________________________________________     ##STR94##                                                                    Comp.                                 n.sub.D.sup.30                          No. R.sup.50                                                                         R.sup.51                                                                         R.sup.52                                                                         R.sup.53                                                                          R.sup.54                                                                         R.sup.55                                                                         R.sup.56                                                                         R.sup.57                                                                          R.sup.58                                                                              or m.p.                                 __________________________________________________________________________     1F CH.sub.3                                                                         H  H  H   H  H  H  H   H       35-42° C.                         2F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   H       47-53° C.                         3F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Br      oil                                      4F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CN      oil                                      5F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-NO.sub.2                                                                        H       oil                                      6F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  5-Cl                                                                              H       oil                                      7F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CH.sub.3 SO.sub.2                                                                     oil                                      8F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CH.sub.3 SO.sub.2                                                                     oil                                      9F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-Cl                                                                              H       oil                                     10F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     11F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     12F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                                                            oil                                     13F CH.sub.3                                                                         H  H  H   H  H  H  H   CH.sub.3 SO.sub.2                                                                     oil                                     14F CH.sub.3                                                                         H  H  H   H  H  H  H   n-C.sub.3 H.sub.7 SO.sub.2                                                            oil                                     15F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CH.sub.3 S                                                                            oil                                     16F C.sub.2 H.sub.5                                                                  CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Br      oil                                     17F CH.sub.3                                                                         H  H  H   H  H  H  H   CN      oil                                     18F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   F       oil                                     19F CH.sub.3                                                                         H  H  H   H  H  H  H   C.sub.2 H.sub.5SO.sub.2                                                               oil                                     20F CH.sub.3                                                                         H  H  H   H  H  H  3-Cl                                                                              H       65-67° C.                        21F CH.sub.3                                                                         H  H  H   H  H  H  3-I H       oil                                     22F CH.sub.3                                                                         H  H  H   H  H  H  3-NO.sub.2                                                                        H       oil                                     23F CH.sub.3                                                                         H  H  H   H  H  H  3-CN                                                                              H       96-101° C.                       24F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   H       oil                                     25F CF.sub.3                                                                         H  H  H   H  H  H  H   H       oil                                     26F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Br      oil                                     27F CF.sub.3                                                                         H  H  H   H  H  H  H   Cl      82-88° C.                        28F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   Cl      oil                                     29F CF.sub.3                                                                         H  H  H   H  H  H  H   C.sub.2 H.sub.5 S                                                                     oil                                     30F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     31F CF.sub.3                                                                         H  H  H   H  H  H  H   CN      oil                                     32F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CN      oil                                     33F.sup.a)                                                                        CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   Br      oil                                     34F CH.sub.3                                                                         H  H  H   H  H  H  H   CH.sub.3                                        35F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-Cl                                                                              C.sub.2 H.sub.5 SO.sub.2                                                              115-117° C.                      36F CH.sub.3                                                                         H  H  H   H  H  H  3-Cl                                                                              C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     37F CH.sub.3                                                                         b) b) H   H  H  H  3-CF.sub.3                                                                        H       oil                                     38F CH.sub.3                                                                         c) H  i-C.sub.3 H.sub.7                                                                 H  H  H  3-NO.sub.2                                                                        H       88-108° C.                       39F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CH.sub.3 S                                                                            oil                                     40F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CH.sub.3 S                                                                            oil                                     41F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CH.sub.3 SO.sub.2                                                                     oil                                     42F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CF.sub.3                                                                              oil                                     43F CH.sub.3                                                                         H  H  H   H  H  H  H   CF.sub.3                                                                              114-120° C.                      44F CH.sub.3                                                                         H  H  H   H  H  H  3-Cl                                                                              Cl      oil                                     45F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-Cl                                                                              Cl      oil                                     46F CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  3-CF.sub.3                                                                        H       oil                                     47F CF.sub.3                                                                         H  H  H   H  H  H  H   CH.sub.3 S                                                                            oil                                     48F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   CF.sub.3                                                                              oil                                     49F CF.sub.3                                                                         H  H  H   H  H  H  H   CF.sub.3                                                                              oil                                     50F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  H  H  H   CF.sub.3                                                                              oil                                     51F CH.sub.3                                                                         H  H  CH.sub.3                                                                          H  H  H  H   CH.sub.3 SO.sub.2                                                                     oil                                     52F CF.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H   H  CH.sub.3                                                                         H  H   C.sub.2 H.sub.5 SO.sub.2                                                              oil                                     53F CH.sub.3                                                                         H  H  H   H  H  H  H   Br      94-98° C.                        54F CH.sub.3                                                                         H  H  H   H  H  H  d)  H       oil                                     __________________________________________________________________________     .sup.a) Prepared in Example 1F,F'.                                             b) (CH.sub.2).sub.5                                                           c) C.sub.2 H.sub.5 OC(O)-                                                     d) 3N(CH.sub.3)COCH.sub.3                                               

                                      TABLE I-G                                   __________________________________________________________________________     ##STR95##                                                                    Comp.                                                                         No. R.sup.60                                                                           R.sup.61                                                                         R.sup.62                                                                         R.sup.63                                                                         R.sup.64                                                                         R.sup.65                                                                           R.sup.66                                                                              m.p. °C.                             __________________________________________________________________________     1G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    H       112-117                                     .sup.  2G.sup.a)                                                                  NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-Cl    76-82                                        3G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 CH.sub.3                                                                   .sup. 176-179°                        4G CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 C.sub.2 H.sub.5                                                            gum                                          5G CF.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CF.sub.3                                                                            viscous oil                                  6G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 CH.sub.2 Cl                                                                oil                                          7G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-F     gum                                          8G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-OC.sub.2 H.sub.5                                                                 4-SO.sub.2 C.sub.2 H.sub.5                                                            gum                                          9G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 CH.sub.3                                                                   gum                                         10G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SCH.sub.3                                                                           gum                                         11G CH.sub.3                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-NO.sub.2                                                                         H       gum                                         12G I    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    H       gum                                         13G OCH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-Cl    gum                                         14G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-OCH.sub.3                                                                        4-Br    gum                                         15G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 nC.sub.3 H.sub.7                                                           gum                                         16G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2 N(CH.sub.3).sub.2                                                          gum                                         17G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CN    .sup. 148-150°                       18G SO.sub.2 CH.sub.3                                                                  CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    H       gum                                         19G NO.sub.2                                                                           CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CF.sub.3                                                                            gum                                         20G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-Cl    gum                                         21G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SCF.sub.3                                                                           gum                                         22G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-OCF.sub.3                                                                           gum                                         23G Cl   CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         3-Cl 4-SO.sub.2 C.sub.2 H.sub.5                                                            gum                                         24G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-C(O)CH.sub.3                                                                        gum                                         25G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SO.sub.2CH.sub.3                                                                    129-131                                     26G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-SCH.sub.3                                                                           89-92                                       27G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CF.sub.3                                                                            115-125                                     28G H    CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3                                                                         H    4-CN    87-95                                       __________________________________________________________________________     .sup.a) prepared in Example 1G,G'.                                       

Herbicidal Screening Tests

As previously mentioned, the herein described compounds produced in theabove-described manner are phytotoxic compounds which are useful andvaluable in controlling various plant species. Selected compounds ofthis invention were tested as herbicides in the following manner.

Pre-emergence herbicide test. On the day preceding treatment, seeds ofeight different weed species are planted in loamy sand soil inindividual rows using one species per row across the width of a flat.The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG)(Echinochloa crusgalli), wild oat (WO) (Avena fatua), annualmorningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilontheophrasti), Indian mustard (MD) (Brassica juncea), redroot pigweed(PW) (Amaranthus retroflexus) or curly dock (CD) (Rumex crispus), andyellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted togive about 20 to 40 seedlings per row, after emergence, depending uponthe size of the plants.

Using an analytical balance, 600 milligrams (mg) of the compound to betested are weighed out on a piece of glassine weighing paper. The paperand compound are placed in a 60 milliliter (ml) wide-mouth clear bottleand dissolved in 45 ml of acetone or substituted solvent. Eighteen ml ofthis solution are transferred to a 60 ml wide-mouth clear bottle anddiluted with 22 ml of a water and acetone mixture (19:1) containingenough polyoxyethylene sorbitan monolaurate emulsifier to give a finalsolution of 0.5% (v/v). The solution is then sprayed on a seeded flat ona linear spray table calibrated to deliver 80 gallons per acre (748L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).

After treatment, the flats are placed in the greenhouse at a temperatureof 70° to 80° F. and watered by sprinkling. Two weeks after treatment,the degree of injury or control is determined by comparison withuntreated check plants of the same age. The injury rating from 0 to 100%is recorded for each species as percent control with 0% representing noinjury and 100% representing complete control.

The results of the tests are shown in the following Tables.

                                      TABLE II-A                                  __________________________________________________________________________    Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd. No.                                                                           FT WG WO  AMG VL  MD PW CD YNS                                          __________________________________________________________________________     1A   100                                                                              90 20  40  65  50 35    80                                            2A   80 90  0  30  80  90 20    90                                            3A    0  0  0  40  40  40  0     0                                            4A   100                                                                              100                                                                              50  35  100 100                                                                              90    95                                            5A   100                                                                              95 65  35  90  85 50    95                                            6A   50 25  0  25  100 100                                                                              35    80                                            7A   80 90 10  60  100 100                                                                              100   80                                            8A   95 95 45  40  100 80 95    95                                            9A   95 100                                                                              55  30  100 90 100   95                                           10A   100                                                                              100                                                                              60  20  85  100                                                                              100   95                                           11A   85 100                                                                              30  40  100 100                                                                              100   95                                           12A   85 85 90  75  80  95 90    90                                           13A   85 75 10  10  85  65 95    90                                           14A   40 10 80   0  65  40 65    100                                          15A   40 60 20  30  100 30 75    95                                           16A   80 80 20  55  75  90 40    95                                           17A   20 -- 10  25  100 95 85    90                                           18A   65 -- 30  70  100 100                                                                              85    90                                           19A   45 60  0  30  40   0 20    60                                           20A   30 85 20  40  95  85 40    45                                           21A   80 100                                                                               0  80  100 100                                                                              95    95                                           22A   20 10  0  20  75  30 45    10                                           23A   45 95 10   0  100 85 100   95                                           24A   -- 100                                                                               0  25  70  90 --    100                                          25A   -- 100                                                                              25  80  100 100                                                                              --    100                                          26A   40 15  0   0   0  10     0 30                                           27A   40 80 10  20  60  50    30 75                                           28A   65 75  0  65  100 95    75 55                                           29A   100                                                                              95 55  10  80  75    85 95                                           30A   20 20 20  10  40  40    50 20                                           31A   75 95 20  20  100 95    75 10                                           32A   90 85 20   0  100 85    75 30                                           33A   80 70  0  40  20  40    90 80                                           34A   60 40  0  20  95  100   100                                                                              60                                           35A    0 10  0   0  10  20    20 10                                           36A    0  0  0  20  100 100   100                                                                               0                                           37A   40  0  0  20  100 60    90 --                                           38A   10 40  0  20  90  80    20 20                                           39A   80 10  0   0   0   0     0 90                                           40A   60  0  0   0   0   0     0 90                                           41A   100                                                                              100                                                                              85  40  95  100   100                                                                              100                                          42A   60 100                                                                              25   0   0   0     0 25                                           43A   100                                                                              100                                                                              45  40  80  90    90 100                                          44A   90 100                                                                               0  60  100 100   100                                                                              95                                           45A   100                                                                              100                                                                               0  60  100 100   100                                                                              100                                          46A   20 60  0  100 100 100   100                                                                              20                                           47A   60 70 20  100 100 100   100                                                                              60                                           48A   60  0  0   0   0   0     0 40                                           49A   100                                                                              100                                                                              50  10  60  20    90 100                                          50A   100                                                                              100                                                                              80  10  60  60    90 100                                          51A   100                                                                              100                                                                              90  100 100 100   85 100                                          52A   100                                                                              100                                                                              60  10  100 100   60 100                                          53A    0 20  0   0  20  20     0 10                                           54A   10 45 10   0   0   0     0 40                                           55A   90 100                                                                              60  100 100 100   90 100                                          56A   40 70 40  40  40  60    70 50                                           57A   100                                                                              100                                                                              90  100 100 100   85 100                                          58A   90 95  0  20  20  40    40 100                                          59A   95 100                                                                              85  75  100 100   90 98                                           60A   95 100                                                                              50  50  100 100   90 98                                           61A   100                                                                              100                                                                              75  100 100 100   95 95                                           62A   100                                                                              100                                                                              95  75  100 100   100                                                                              80                                           63A   100                                                                              100                                                                              40  65  100 100   100                                                                              95                                           64A   100                                                                              100                                                                              98  100 100 100   100                                                                              90                                           65A   100                                                                              100                                                                              80  100 100 100   100                                                                              90                                           66A   100                                                                              100                                                                              75  100 100 100   100                                                                              98                                           73A   100                                                                              100                                                                              60  80  100 100   75 90                                           74A   100                                                                              100                                                                              70  80  100 100   80 100                                          75A   70 100                                                                               0  50  100 100   100                                                                              80                                           76A   40 90 25  10  100 100   100                                                                              10                                           77A   100                                                                              100                                                                              90  100 100 100   85 --                                           78A   100                                                                              100                                                                              80  100 100 100   90 --                                           79A   50 100                                                                              50  50  95  100   100                                                                              60                                           80A    0  0  0   0   0   0     0  0                                           81A   100                                                                              100                                                                              50  15  100 100   90 100                                          84A   100                                                                              100                                                                              85   0   0  100   20 100                                          88A   60 95 35  95  100 100   95 80                                           89A   75 100                                                                              40  100 100 100   95 60                                           90A   100                                                                              100                                                                              90  100 100 100   100                                                                              85                                           105A  80 95 25   0  95  50    70 50                                           117A  95 100                                                                               0  25  100 100   50 95                                           118A  100                                                                              100                                                                              60  100 100 100   100                                                                              85                                           121A  95 100                                                                              50  75  100 95    100                                                                              80                                           125A  100                                                                              100                                                                              50  80  100 100   100                                                                              85                                           126A  70 100                                                                              80  80  100 100   100                                                                              80                                           127A  100                                                                              100                                                                              100 100 100 100   -- 80                                           128A  100                                                                              100                                                                              100 100 100 100   -- 80                                           129A  100                                                                              100                                                                              95  90  100 100   -- 80                                           131A  70 85  0  20  95  98    95 90                                           132A  100                                                                              100                                                                              95  90  100 100   -- 80                                           133A  100                                                                              100                                                                              100 100 100 100   -- 80                                           135A  100                                                                              100                                                                              100 80  100 100   -- 80                                           __________________________________________________________________________

                  TABLE II-B                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                         1B    0      85      10   75   100   80    80   75                            2B    90    100      65  100   100  100   100  100                            4B   100    100      80   60   100   80    90  100                            5B    80    100      20   40   100  100    80  100                            6B    40    100      0    40   100  100    80  100                            7B   100    100     100   80   100  100    90  100                            8B   100    100      60   45    60   60    80  100                            9B    60    100      40   20    60   60    60  100                           10B   100    100      40   5     80   60    80  100                           11B   100    100      90   10    20   20    40  100                           12B    0      20      0    0     10   20    10   0                            13B   100    100      90   40   100  100   100  100                           15B    90     90      50   20   --   100   100   80                           16B   100    100      95  100   100  100    90  100                           17B   100    100     100  100   100  100   100   97                           18B   100    100      85  100   100  100    90   95                           19B   100    100      95  100   100  100   100   95                           20B   100    100      85  100   100  100   100   90                           21B   100    100     100  100   100  100   100   95                           22B   100    100      80  100   100  100   100   90                           25B   100    100      75   80   100  100   100   90                           26B   100    100      65   30   100  100   100   90                           27B    20     95      60   5    100  100    90  100                           28B   100    100      80   20    90   40    80  100                           29B   100    100      70   20   100  100   100  100                           30B   100    100      80   60   100  100    80  100                           31B    80    100      40   10    60   60    80  100                           32B    20     40      10   0    --    60   100   60                           33B    0      10      0    0     10   10    0    0                            34B   100    100      90   80   100  100    90  100                           35B   100    100      90   40    90   90    90   90                           36B   100    100      85   0     95   85    95   90                           37B    90     90      50   20   --   100   100   80                           39B    15    100      0    50   100   80    70   40                           40B    0      10      0    0     10   10    0    0                            41B    0      20      0    0     10   20    10   0                            42B   100    100      90   45   100  100    65  100                           43B   100    100      90  100   100  100   100   90                           44B   100    100      85  100   100  100   100   95                           45B    65    100      0    0    100   20    20   90                           46B   100    100      0    20   100  100    98   85                           47B   100    100      90   85   100  100   100   95                           48B   100    100      85   15   100  100    85   95                           49B   100    100      65   0    100  100    50   50                           50B    80     80      55   0     98   55    80   65                           51B    95     95      10   0     65   0     25   60                           52B   100    100     100  100   100  100   100   50                           53B   100    100      75  100   100  100   100   50                           54B   100    100      60   15   100  100   100   80                           55B   100    100      55   15   100  100    90   95                           56B   100    100      60   20    95  100    90   10                           57B    5      10      0    0     40    20   0    0                            58B    10     40      10   10    95   40   100   80                           59B   100    100      75   80   100  100   100   75                           60B   100    100      90  100   100  100    85  --                            61B   100    100      80  100   100  100   100  --                            62B   95     100      50   95   100  100    85  --                            63B   100    100      70  100    90  100   100  --                            64B   100    100      75  100   100  100    85  --                            65B   100    100      55   40   100  100    90   70                           66B   100    100      65   35   100  100   100   95                           67B   100    100      30   15   100  100    95   90                           71B   100    100      80  100   100  100    80  --                            72B   100    100      40  100   100  100    90   75                           73B    90    100      40  100   100  100    95   50                           74B   100    100      85   95   100  100    90   80                           75B   100    100     100   70   100  100   100   95                           77B   100    100      55   40   100  100    90   70                           81B    90     95      60   10    25   75    90   0                            82B    40     90      20   35   100  --     75   20                           91B   100    100      85  100   100  100    80   90                           101B   85     90      0    0     95   50    50   75                           ______________________________________                                    

                  TABLE II-C                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd. No.                                                                             FT     WG     WO   AMG   VL   MD   CD   YNS                           ______________________________________                                        1C      65     80     65   55    90   90   35   0                             ______________________________________                                    

                  TABLE II-D                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                         1D   100    100     85   30    100  100   90   90                             2D   100    100     100  50    100  100   95   95                             3D   100    100     85   25    100  100   100  95                             4D   100    100     100  20    100   85   95   90                             5D   100    100     45   25    100  100   90   90                             6D   100    100     95   40    100  100   85   90                             9D   100    100     90   90    100  100   80   90                            10D   100     90     20   10    100   70   100  90                            11D    90    100     50   230   100  100   90   90                            12D   100    100     95   80    100  100   90   90                            13D    40     75      0   10     80  100   100  90                            14D    50     0       0    0    100   80   70   90                            15D    65     95     20   15    100   80   90   85                            17D   100    100     60   30    100  100   90   35                            18D   100    100     100  100   100  100   100  95                            19D   100    100      0   50    100  100   100  95                            20D    75    100      0   25    100   90   65   90                            21D   100    100     100  80    100  100   90   95                            22D   100    100     100  80    100  100   95   95                            23D   100    100     98   95    100  100   100  95                            25D   100    100     80   100   100  100   80   --                            26D   100    100     75   100   100  100   80   --                            27D    90    100     50   100   100  100   100  90                            28D    75     50     50    0    100  100   90   65                            30D   100    100     85   100   100  100   95   90                            31D    85     75      0   25    100   25    0   35                            32D    83     85     35   20     95  100   75   50                            36D   100    100     50   100   100  100   100  75                            37D    20      75     0   20    100  95    100  75                            38D    85     95     40   60    100  100   75   85                            39D    85     95     45   75    100   95   70   90                            51D    60     60     35    0     25   0     0   30                            52D    75     75      0   50     90   75   40    0                            65D   100    100     80   100   100  100   --   80                            ______________________________________                                         A blank (--) indicates that the weed was not tested.                     

                  TABLE II-E                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                        1E     0      0       0    0     0    0     0   20                            2E     25     30     30    0     70   0    40   30                            3E     25     20      0    0     0    0     0    0                            4E    100    100     90   60    100  100   100  90                            5E     50     60     40   50     50  60    90   50                            6E    100     95     50   40     40  60    99   70                            16E    80    100     50   60    100  90    90   90                            20E   100    100     30   15    100  100   90   85                            21E   100    100     --   30    100  95    100  80                            ______________________________________                                         A blank (--) indicates that the weed was not tested.                     

                  TABLE II-F                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                         1F    40     20      0    0     0    0     0   100                            2F    60     70      0    0     0    0     90  100                            3F   100    100     50   50    100  100    85  90                             4F   100    100     90   30    100   85    95  95                             5F   100    100     80   10    100  100   100  95                             6F    20     35     25   15     90   85    40  85                             7F   100    100     90   100   100  100   100  95                             8F   100    100     90   100   100  100   100  95                             9F   100    100      0    0    100   80   100  90                            10F   100    100     100  100   100  100   100  95                            11F   100    100     70   100   100  100    97  95                            12F   100    100     60   100   100  100   100  95                            13F   100    100     60   100   100  100   100  95                            14F    80    100     50   80    100  100    90  90                            15F   100    100     80   100   100  100   100  --                            16F    50     75      0   25    100  100    95  60                            17F   100    100     40   100   100  100   100  85                            18F   100    100      0   20    100  100    80  70                            20F    70     75      0   25    100   95   100  60                            21F    50     60      0    0    100   80    80  60                            22F   100     95     35   25    100  100    90  50                            23F    95    100     40   20    100  100    90  50                            24F   100    100     90    0     45   85    80  90                            25F   100    100     25   60    100  100   100  75                            34F    35     40     10    0     60   25    0   70                            37F    50     60      0    0     60   0     50    0                           38F    35     40      0    0     0    0     0    0                            52F    85    100     30   95    100  100   --   80                            53F   100    100      0   85    100  100   --   80                            54F   100    100     90   25    100  100   --   80                            ______________________________________                                         A blank (--) indicates that the weed was not tested.                     

                  TABLE II-G                                                      ______________________________________                                        Pre-Emergence Herbicidal Activity                                             Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT       WG     WO    AMG   VL    MD   YNS                              ______________________________________                                         1G   100      100    90    100   100   100  80                                2G   100      100    90    100   100   100  80                                3G   100      100    90    100   100   100  80                                4G   100      100    90    100   100   100  80                                5G   100      100    90    100   100   100  80                                6G*  100      100    100   100   100   --   20                                7G   100      100    80    100   100   100  80                                8G    85      100    80    100   100   100  80                                9G   100      100    80    100   100   100  80                               10G   100      100    80    100   100   100  80                               11G   100      100    80    100   100   100  80                               12G   100      100    80     90   100   100   0                               13G   100      100    70    100   100   100   0                               14G   100      100    75    100   100   100  90                               15G   100      100    80    100   100   100  90                               16G   100      100    90    100   100   100  80                               17G   100      100    80    100   100   100  80                               18G   100      100    90     85   100   100  80                               19G   100      100    100   100   100   100  80                               20G    70       95    10    100   100   100   0                               21G   100      100    100   100   100   100  80                               22G   100      100    90    100   100   100  80                               23G   100      100    100   100   100   100  80                               24G    0        80     0     25    80    70   0                               25G   100      100    80    100   100   100  80                               26G   100      100    100    80   100   100  80                               27G   100      100    100   100   100   100  80                               28G   100      100    90    100   100   100  80                               ______________________________________                                         A blank (--) indicates that the weed was not tested.                          *Tested at 0.56 kg/ha.                                                   

Post-Emergence Herbicide Test: This test is conducted in an identicalmanner to the testing procedure for the pre-emergence herbicide test,except the seeds of the eight different weed species are planted 10-12days before treatment. Also, watering of the treated flats is confinedto the soil surface and not to the foliage of the sprouted plants.

The results of the post-emergence herbicide test are reported in TableIII.

                                      TABLE III-A                                 __________________________________________________________________________    Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd. No.                                                                           FT WG WO  AMG VL  MD PW CD YNS                                          __________________________________________________________________________     1A   60 70 20  40  60  60 35    60                                            2A   30 70  0  50  90  85 30    80                                            3A    0 30  0  70  100 90 55    70                                            4A   95 98 20  98  100 100                                                                              30    95                                            5A   80 80 75  50  60  80  0    95                                            6A   40 40 10  60  100 100                                                                              75    65                                            7A   60 75 40  60  100 75 100   75                                            8A   85 80 75  70  95  80 90    90                                            9A   85 80 75  70  95  80 90    90                                           10A   95 85 90  60  95  95 80    95                                           11A   50 80 35  55  100 100                                                                              95    80                                           12A   45 75 50  55  75  60 50    80                                           13A   30 60 20  60  80  50 60    70                                           14A   20 10 20  50  45  40 40     0                                           15A   65 95  0  65  95  30 100   80                                           16A   65 80 20  85  85  30 30    80                                           17A   75 80 30  70  100 100                                                                              85    90                                           18A   100                                                                              95 10  100 100 100                                                                              100   90                                           19A   60 80 40  70  100 75 80    90                                           20A   65 80 10  85  95  95 100   70                                           21A   30 55  0  80  100 80 65    80                                           22A    0 30  0  20  45   0 30    20                                           23A   85 90 40  85  100 95 100   90                                           24A    0 80  0  70  90  74 --    100                                          25A   100                                                                              100                                                                              75  90  100 100                                                                              --    100                                          26A   45 30  0  40  70  65     0 45                                           27A   75 80 30  65  50  45    85 85                                           28A   75 60 60  75  100 70    80 25                                           29A   85 85 85  75  85  65    65 85                                           30A   75 50 20  10   0   0    20 40                                           31A   60 60 20  40  40  70    100                                                                              40                                           32A   60 25 20  40  90  65    20 40                                           33A   10  0  0  10  10  10    100                                                                              40                                           34A   10 10  0   5  50  30    80  0                                           35A    0  0  0  10  60  30    40  0                                           36A    0  0  0  20  20  20     0  0                                           37A    0  0  0  30  40  20    80  0                                           38A   10 10 10  20  10  20    20 10                                           39A   40 40 20   0   0   0     5 80                                           40A   90 70 40  20  60  80    20 65                                           41A   60 85 85  20  40  60    100                                                                              100                                          42A   60 50 40  70  20  40    60 60                                           43A   100                                                                              80 30  60  100 100   80 100                                          44A   80 85  0  60  90  90    100                                                                              80                                           45A   90 90 10  100 100 100   100                                                                              90                                           46A   80 100                                                                               0  60  100 100   100                                                                              100                                          47A   100                                                                              100                                                                               0  60  100 100   100                                                                              100                                          48A   40 40 20  10  10  10    90 40                                           49A   40 40 40  80  100 100   60 60                                           50A   80 60 60  50  50  60    80 70                                           51A   80 80 80  95  100 100   100                                                                              90                                           52A   60 60 20  20  40  40    90 60                                           53A   10 20 20   0   0   0     0 20                                           54A   20 40 20   5   0   0     0 40                                           55A   40 40 40  60  60  60    80 90                                           56A   100                                                                              100                                                                              75  80  100 100   100                                                                              90                                           57A   80 80 80  95  100 100   100                                                                              90                                           58A   60 70 10  70  10  10    20 80                                           59A   100                                                                              100                                                                              90  100 --  100   100                                                                              50                                           60A   100                                                                              100                                                                              100 100 --  100   100                                                                              70                                           61A   90 85 90  85  --  100   100                                                                              80                                           62A   100                                                                              85 100 75  100 100   100                                                                              35                                           63A   70 80 20  100 100 100   35 40                                           64A   75 75 90  70  90  70    40 40                                           65A   100                                                                              70 100 55  90  95    100                                                                              40                                           66A   100                                                                              75 100 90  95  95    100                                                                              20                                           73A   100                                                                              100                                                                              95  100 100 100   55 30                                           74A   100                                                                              95 75  100 100 100   85 40                                           75A   100                                                                              100                                                                              30  95  80  100   80 40                                           76A   80 80 75  75  100 95    95 25                                           77A   80 80 80  90  90  80    90 80                                           78A   80 85 75  85  80  95    100                                                                              50                                           79A   50 65 35  90  100 100   90 --                                           80A   40 40 10  20  60   0     0 30                                           81A   90 70 60  40  60  60    90 70                                           84A   100                                                                              100                                                                              100 20  40  40    80 60                                           88A   100                                                                              95 90  100 85  100   100                                                                              50                                           89A   100                                                                              100                                                                              75  85  75  85    95 50                                           90A   100                                                                              85 90  90  85  90    100                                                                              55                                           91A   100                                                                              100                                                                              100 100 95  100   95 60                                           105A  35 50 --  35  100 80    60 30                                           117A  40 60  0  25  50  50    80 --                                           118A  95 85 85  100 100 90    80 80                                           121A  65 85 40  100 100 100   60 50                                           125A  90 95 75  70  100 90    100                                                                              60                                           126A  40 50 20  40  60  50    100                                                                              80                                           127A  100                                                                              95 100 95  100 100      80                                           128A  85 95 80  60  100 95       80                                           129A  65 90 60  60  100 98       70                                           130A  100                                                                              95 95  95  100 100      70                                           131A   0 20  0   0  30  75    10  0                                           132A  95 100                                                                              100 80  95  95       50                                           133A  80 95 90  60  85  85       60                                           135A  70 100                                                                              100 75  100 95       70                                           __________________________________________________________________________

                  TABLE III-B                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                         1B   85     95      20   95    100  100   95   95                             2B   90     90      80   100   90   90    --   80                             4B   60     60      90   40    60   60    90   70                             5B   40     60      10   20    40   40    90   80                             6B   40     50      10   60    20   20    60   50                             7B   80     80      80   60    60   90     6   60                             8B   100    80      60   30    80   80    80   80                             9B   70     70      60   40    60   60    80   70                            10B   40     40      60   30    60   60    90   60                            11B   80     90      60   45    90   90    100  80                            12B   25     45      10   20    20   20    60   45                            13B   100    100     95   70    60   60    80   60                            15B   100    60      50   80    90   90    40   60                            16B   60     60      80   80    90   90    60   65                            17B   100    70      90   100   --   90    98   70                            18B   100    85      100  85    --   100   100  65                            19B   100    80      85   100   100  90    100  70                            20B   90     65      90   85    70   60    100  40                            21B   40     40      10    0     0    0     0    0                            22B   40     70      80   90    90   100   95   40                            25B   40     70      40   40    40   60    70   50                            26B   65     70      80   40    90   80    70   80                            27B   100    80      60   20    90   90    80   45                            28B   90     60      60   60    60   60    40   70                            29B   90     70      70   40    70   70    60   60                            30B   100    90      70   50    100  100   80   80                            31B   40     50      20   10    20   20     0   40                            32B   25     40      40   90    100  100   40   40                            33B   20     40      10   60    90   90    60   40                            34B   90     80      80   80    100  100   80   50                            35B   60     50      50   20    60   60    80   60                            36B   100    80      80   75    --   100   100  45                            37B   100    60      50   80    90   90    40   60                            39B   90     80      25   30    30   45    50   30                            40B   20     40      10   60    90   90    60   40                            41B   25     45      10   20    20   20    60   45                            42B   90     80      80   80    100  100   100  70                            43B   80     90      95   97    100  100   100  50                            44B   100    95      95   95    40   100   100  30                            45B   30     65       0   30    45   40    65   50                            46B   70     75       0   65    100  100   50   70                            47B   100    100     100  90    100  100   100  85                            48B   100    65      80   50    100  100   60   60                            49B   60     70      70   40    80   70    30   50                            50B    0     60      40   60    100  90    20   30                            51B   100    75      80   40    100  50    20   30                            52B   90     100     100  100   100  100   100  40                            53B   60     70      70   70    90   65    40   60                            54B   100    100     85   100   100  100   100  60                            55B   95     85      90   100   100  100   90   45                            56B   85     100      0   10    15   95    40   50                            57B   85     70      65    0     0    0     0   35                            58B   20     40      10   15    70   40    35   40                            59B   100    95      100  95    100  95    100  40                            60B   65     75      75   80    90   85    80   60                            61B   80     80      70   95    80   85    80   50                            62B   100    80      25   80    75   80    85   35                            63B   100    100     40   95    95   100   95   50                            64B   75     70      50   90    90   100   90   50                            65B   100    80      80   60    85   60     0   --                            66B   98     90      60   35    --   100   60   90                            67B   70     65      20   15    95   40    70   45                            71B   95     50      50   80    80   80    65   50                            72B   100    85      75   75    65   85    70   60                            73B   100    95      95   85    75   85    95   40                            74B   100    85      95   90    80   95    65   50                            75B   100    80      80   30    50   60    100  40                            81B   50     80      35   70    70   90    80   10                            82B   25     60      50   35    50   90    50   25                            91B   80     60      40   60    75   90    60   75                            101B  10     35      --   30    75   70    40   50                            ______________________________________                                         (--) = Specie did not germinate for some reason.                         

                  TABLE III-C                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd. No.                                                                             FT     WG     WO   AMG   VL   MD   CD   YNS                           ______________________________________                                        1C      98     95     70   60    100  55   100  90                            ______________________________________                                    

                  TABLE III-D                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG      WO   AMG   VL   MD    CD   YNS                           ______________________________________                                         1D   95     75      85   70    100  90    85   40                             2D   45     70      95   75    100  90    100  65                             3D   100    80      100  90    --   100   100  80                             4D   100    80      100  100   --   100   85   75                             5D   90     70      45   60    95   70    60   80                             6D   95     75      80   70    100  90    90   65                             9D   100    90      90   100   100  100   95   85                            10D   45     75      10   15    100  100   20   75                            11D   100    70      60   75    100  100   100  45                            12D   100    75      100  100   100  100   90   90                            13D   30     55       0   30    60   60    15   60                            14D   20     65       0   40    70   60    40   25                            15D   20     75      30   20    100  70    60   40                            17D   85     80      50   65    95   95    100  60                            18D   100    95      100  100   100  100   100  75                            19D   20     95      30   100   100  35    30   70                            20D   30     80      15   100   100  45    20   70                            21D   100    80      100  55    100  90    100  80                            22D   100    80      100  60    100  95    95   95                            23D   100    90      90   100   100  100   85   70                            25D   70     75      50   85    90   85    60   75                            26D   100    85      85   95    95   95    90   60                            27D   90     90      60   100   100  100   100  --                            28D   15     45      20   50    75   80    15   30                            30D   100    100     80   85    85   85    100  --                            31D   80     90      100  100   100  100   100  60                            32D   75     85      85   75    75   90    95   50                            36D   35     50      35   70    50   50    35   60                            37D   60     75      15   70    70   90    90   40                            38D   95     90      65   70    90   90    100  50                            39D   95     85      30   50    70   80    100  50                            51D   60     75      60   35    30   60    40   60                            52D   60     75      25   100   100  100   100  75                            65D   70     50      70   90    80   85    --   80                            ______________________________________                                         A blank (--) indicates the weed was not tested.                          

                  TABLE III-E                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG   VL   MD    CD   YNG                            ______________________________________                                        1E    20     20     10   20    40   40    20   40                             2E     0     60     60   50    70   30     0   15                             3E    20     20      0   10     0   20     0   20                             4E    85     90     100  45    75   30    80   65                             5E    55     50     60   50    75   85    65   --                             6E    70     70     50   60    80   70    90   --                             16E   95     95     40   100   100  100   100  90                             20E   95     75     35   40    95   75    35   80                             21E   80     70     30   45    80   90    50   70                             ______________________________________                                         A blank (--) indicates the weed was not tested.                          

                  TABLE III-F                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT     WG     WO   AMG   VL   MD    CD   YNG                            ______________________________________                                         1F   60     40     20   30    40   40    50   60                              2F   50     40     10   20    20   20    40   60                              3F   100    100    85   100   100  100   100  75                              4F   100    100    95   85    100  95    100  60                              5F   95     95     100  65    90   25    70   45                              6F   40     30      0   20    90   25    20   70                              7F   100    100    100  100   100  100   100  90                              8F   100    95     100  100   100  100   100  70                              9F   65     65      0   20    80   65    90   80                             10F   100    100    100  100   100  100   100  70                             11F   85     90     90   85    90   80    30   60                             12F   100    90     65   80    100  100   100  50                             13F   100    95     100  100   100  100   90   --                             14F   100    100    100  100   100  100   100  50                             15F   25     35     15   30    80   25    20    0                             16F   100    85     70   75    90   90    50   --                             17F   100    100    100  100   100  100   100  --                             18F   90     85     85   85    90   95    70   40                             20F   40     60     10   60    100  100   100  50                             21F   35     60     10   60    100  100   80   60                             22F   95     95     35   100   100  100   90   50                             23F   100    100    40   100   100  100   90   50                             24F   100    75     100  60    --   100   100  60                             25F   95     95     90   95    100  100   95   35                             34F   50     40      0   35    50   70    30   50                             37F   20     60      0   30    30   50    50   50                             38F   25     50      0   25    25   50    20   20                             52F    0     60     50   50    10   50    --   20                             53F    0     50      0   50    50   50    --   30                             54F   90     75     60   50    50   80    --   80                             ______________________________________                                         A blank (--) indicates the weed was not tested.                          

                  TABLE III-G                                                     ______________________________________                                        Post-Emergence Herbicidal Activity                                            Application Rate - 4.48 kg/ha                                                 Cmpd.                                                                         No.   FT      WG      WO   AMG   VL    MD    YNG                              ______________________________________                                         1G   100     95      90   90    100   100   80                                2G   100     100     100  100   100   100   80                                3G   100     100     95   100   100   100   90                                4G   100     100     100  100   100   100   90                                5G   100     100     100  100   100   100   100                               6G*  10      80      50   75    40    --    0                                 7G   70      75      70   90    90    80    80                                8G   50      80      70   90    90    80    30                                9G   70      80      70   90    90    80    30                               10G   75      80      70   80    60    50    70                               11G   70      80      70   80    80    80    80                               12G   100     75      90   75    80    80    80                               13G   60      70      70   100   100   100   80                               14G   20      70      40   60    80    80    70                               15G   90      70      70   75    80    90    70                               16G   50      70      80   60    80    90    70                               17G   90      60      70   65    80    80    80                               18G   30      50      80   95    95    80    70                               19G   100     100     95   90    100   100   80                               20G   10      40      5    70    80    90    70                               21G   95      90      95   95    100   100   70                               22G   80      90      90   80    100   100   70                               23G   90      80      80   80    90    80    30                               24G   0       30      0    40    80    20    0                                25G   0       20      0    10    10    20    0                                26G   80      70      70   80    80    80    70                               27G   90      90      90   80    80    90    60                               28G   70      65      50   80    80    80    70                               ______________________________________                                         A blank (--) indicates the weed was not tested.                               *Tested at 0.56 kg/ha.                                                   

Pre-Emergence Multi-Weed Herbicide Test

Several compounds were evaluated at an application rate of 2 lb/acre(2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for pre-emergence activityagainst a larger number of weed species.

The process was generally similar to the pre-emergence herbicide testdescribed above except that only 300 or 150 milligrams of test compoundwere weighed out and the application rate was 40 gallons per acre.

Redroot pigweed (PW) and curly dock (CD) were eliminated in this testand the following weed species were added:

    ______________________________________                                        Grasses:                                                                             downy brome   Bromus tectorum                                                                              (DB)                                             annual ryegrass                                                                             Lolium multiflorum                                                                           (ARG)                                            rox-orange sorghum                                                                          Sorghum bicolor                                                                              (SHC)                                            hemp sesbania Sesbania exaltata                                                                            (SESB)                                           nightshade    Solanum sp.    (SP)                                             cocklebur     Xattiium sp.   (CB)                                      ______________________________________                                    

The results of the 2.24 kg/ha test are shown in Table IV and the resultsof the 1.12 kg/ha test are shown in Table VI.

Post-Emergence Multi-Weed Herbicide Test

Several compounds were evalated at an application rate of 2 lb/acre(2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for post-emergence activityagainst the larger number of weed species that are used in thepre-emergent multi-herbicide test.

The process was generally similar to the post-emergence herbicide testdescribe above except that only 300 or 150 milligrams of test compoundwere weighed out and the application rate was 40 gallons per acre.

The results of the 2.24 kg/ha test are shown in Table V and the resultsfor the 1.12 kg/ha test are shown in Table VII.

                                      TABLE IV-A                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________    67A 20 90 25  98 80  60 90  45  90  45 20 85 85  15                           68A 65 98 98  100                                                                              100 60 95  100 100 100                                                                              80 100                                                                              95  100                          69A 65 100                                                                              70  100                                                                              100 65 95  100 95  70 65 100                                                                              90  --                           70A 98 100                                                                              100 100                                                                              100 90 98  90  100 90 60 100                                                                              95  80                           71A 60 20 100 100                                                                              100 80 95  35  40  100                                                                              20 90 100 40                           72A 100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 90  100                                                                              60 100                                                                              100 20                           83A 15 45 25  90 15  5  90  45  35  20 0  20 75  --                           86A 20 0  15  60 60  20 70  25  45  100                                                                              20 100                                                                              15  35                           87A 100                                                                              90 85  100                                                                              85  25 30  35  85  100                                                                              85 100                                                                              95  40                           __________________________________________________________________________

                                      TABLE VI-A                                  __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate - 2.24 hg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________    86A 60 100                                                                              50  90 50  60 90  70  100 100                                                                              20 100                                                                              20  --                           87A 95 100                                                                              30  100                                                                              80  70 80  95  100 100                                                                              100                                                                              100                                                                              70  --                           __________________________________________________________________________

                                      TABLE V-A                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________     82A                                                                              35 100                                                                              85  100                                                                              65  60 90  50  90  60 30 97 90  40                            85A                                                                              100                                                                              100                                                                              100 100                                                                              100 85 100 20  10  100                                                                              65 100                                                                              100 30                            92A                                                                              15 20 45  100                                                                              90  40 80  95  95  100                                                                              25 100                                                                              90  40                            93A                                                                              30 75 40  100                                                                              100 60 90  100 100 100                                                                              35 100                                                                              90  40                            94A                                                                              30 70 40  100                                                                              100 30 65  95  85  100                                                                              0  100                                                                              90  30                            95A                                                                              0  0  0   85 60  15 70  65  60  100                                                                              80 90 10  20                            96A                                                                              95 100                                                                              98  100                                                                              100 70 100 100 95  90 80 100                                                                              95  --                            97A                                                                              100                                                                              100                                                                              98  100                                                                              100 100                                                                              100 100 95  100                                                                              70 100                                                                              95  100                           98A                                                                              10 0  0   0  20  25 70  0   20  0  0  80 30  --                            99A                                                                              15 0  0   75 25  0  20  30  60  15 20 30 25  0                            100A                                                                              0  0  0   0  0   0  20  10  0   0  0  15 0   --                           101A                                                                              100                                                                              98 95  100                                                                              100 70 98  100 100 100                                                                              20 100                                                                              95  --                           102A                                                                              25 20 35  100                                                                              100 45 95  70  100 100                                                                              60 100                                                                              90  --                           103A                                                                              80 60 45  100                                                                              100 40 90  65  90  100                                                                              0  100                                                                              95  0                            106A                                                                              100                                                                              100                                                                              60  40 95  35 100 35  90  100                                                                              70 100                                                                              90  --                           107A                                                                              100                                                                              100                                                                              100 100                                                                              100 90 100 100 100 100                                                                              80 100                                                                              95  30                           108A                                                                              100                                                                              100                                                                              100 100                                                                              100 85 100 100 100 100                                                                              30 100                                                                              95  100                          109A.sup.a                                                                        65 20 85  100                                                                              98  60 90  30  50  100                                                                              50 100                                                                              90  100                          110A                                                                              0  60 30  100                                                                              65  25 65  25  30  100                                                                              0  100                                                                              60  0                            111A                                                                              100                                                                              100                                                                              100 100                                                                              100 75 98  100 100 100                                                                              90 100                                                                              --  70                           112A                                                                              100                                                                              100                                                                              90  100                                                                              100 95 100 100 100 100                                                                              100                                                                              100                                                                              --  --                           113A                                                                              65 95 40  100                                                                              100 30 90  70  100 100                                                                              0  100                                                                              --  30                           114A                                                                              70 100                                                                              25  100                                                                              100 40 100 100 100 100                                                                              30 100                                                                              95  80                           115A                                                                              100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 100 100                                                                              45 100                                                                              85  100                          116A                                                                              25 15 20  100                                                                              65  35 65  45  50  100                                                                              0  100                                                                              95  10                           119A                                                                              100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 100 100                                                                              95 100                                                                              95  90                           120A                                                                              100                                                                              100                                                                              100 100                                                                              100 95 100 100 100 100                                                                              100                                                                              100                                                                              90  100                          122A                                                                              80 80 45  100                                                                              60  65 70  100 100 100                                                                              100                                                                              100                                                                              90  100                          123A                                                                              0  100                                                                              50  100                                                                              85  0  60  100 90  100                                                                              80 100                                                                              100 20                           124A                                                                              25 50 65  90 65  0  40  75  80  100                                                                              40 90 80  60                           __________________________________________________________________________     .sup.a application rate was 0.56 kg/ha.                                  

                                      TABLE VII-A                                 __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________     82A                                                                              60 40 10  98 35  10 30  70  100 100                                                                              100                                                                              90 45  --                            85A                                                                              60 60 35  100                                                                              45  60 85  50  100 100                                                                              100                                                                              100                                                                              60  --                            92A                                                                              70 55 20  80 80  45 100 95  90  80 20 95 70  90                            93A                                                                              90 90 70  95 95  75 90  98  95  85 35 100                                                                              60  90                            94A                                                                              100                                                                              85 45  90 100 90 100 100 90  90 30 100                                                                              60  85                            95A                                                                              20 60 0   80 70  0  45  60  75  90 0  65 20  --                            96A                                                                              95 100                                                                              90  95 100 80 95  100 100 100                                                                              70 100                                                                              70  90                            97A                                                                              100                                                                              100                                                                              95  100                                                                              100 100                                                                              100 100 100 100                                                                              90 100                                                                              70  100                           98A                                                                              20 0  0   45 10  50 30  20  65  100                                                                              0  75 35  80                            99A                                                                              25 75 15  80 65  10 25  85  100 100                                                                              80 100                                                                              10  --                           100A                                                                              10 35 0   70 50  5  20  30  70  40 0  100                                                                              10  100                          101A                                                                              30 60 25  100                                                                              60  60 80  100 100 100                                                                              30 100                                                                              70  --                           103A                                                                              90 100                                                                              25  100                                                                              100 80 100 100 100 100                                                                              15 100                                                                              40  --                           104A                                                                              98 98 25  98 100 15 100 100 100 100                                                                              60 100                                                                              95  --                           106A                                                                              75 90 30  90 70  25 100 100 100 100                                                                              80 100                                                                              75  --                           107A                                                                              100                                                                              100                                                                              80  90 85  100                                                                              100 100 100 100                                                                              60 100                                                                              40  --                           108A                                                                              100                                                                              100                                                                              65  90 60  95 100 100 100 100                                                                              90 100                                                                              90  --                           109A.sup.a                                                                        90 60 45  90 70  60 98  95  95  100                                                                              98 80 55  --                           110A                                                                              50 50 20  100                                                                              50  10 40  100 98  98 20 100                                                                              35  45                           111A                                                                              85 90 80  90 70  60 95  100 90  100                                                                              65 100                                                                              80  60                           112A                                                                              100                                                                              100                                                                              90  100                                                                              100 95 100 100 100 100                                                                              45 100                                                                              95  70                           113A                                                                              70 50 20  90 60  50 80  95  95  100                                                                              60 100                                                                              --  60                           114A                                                                              85 100                                                                              15  100                                                                              100 60 00  100 100 100                                                                              100                                                                              100                                                                              60  --                           115A                                                                              100                                                                              100                                                                              45  100                                                                              100 80 100 100 100 100                                                                              100                                                                              100                                                                              90  --                           116A                                                                              80 60 25  90 35  40 45  75  90  100                                                                              40 90 75  60                           119A                                                                              60 70 30  95 70  20 90  100 100 100                                                                              90 100                                                                              30  85                           120A                                                                              75 90 60  95 80  45 100 100 90  100                                                                              65 100                                                                              35  100                          122A                                                                              60 90 15  100                                                                              30  15 15  100 100 100                                                                              75 100                                                                              45  95                           123A                                                                              0  100                                                                              35  100                                                                              50  15 85  100 100 100                                                                              100                                                                              100                                                                              70  85                           124A                                                                              25 100                                                                              35  40 35  0  40  95  100 100                                                                              100                                                                              100                                                                              85  75                           __________________________________________________________________________     A = Application rate was 0.56 kg/ha.                                          A dash mark (--) is used in Tables II-VII to indicate that no percent         control number was available.                                            

                                      TABLE IV-B                                  __________________________________________________________________________    Pre-Emergence Multi-Weed Herbicide Test                                       Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________    14B 80 100                                                                              100 100                                                                              100 80 95  70  60  100                                                                              40 85 100 10                           21B 85 100                                                                              90  100                                                                              100 85 100 100 100 100                                                                              70 100                                                                              95  100                          24B 100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 100 100                                                                              75 100                                                                              95  --                           38B 100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 20  10  100                                                                              20 95 100 20                           88B 75 100                                                                              60  100                                                                              100 70 60  20  40  100                                                                              0  100                                                                              60  20                           89B 20 60 30  85 95  55 40  15  20  65 0  100                                                                              35  50                           90B 60 100                                                                              60  100                                                                              100 45 30  100 100 100                                                                              15 100                                                                              50  85                           103B                                                                              95 100                                                                              75  100                                                                              100 50 85  100 100 100                                                                              80 100                                                                              80  40                           104B                                                                              60 100                                                                              60  100                                                                              100 45 30  100 100 100                                                                              15 100                                                                              50  85                           __________________________________________________________________________     (--) = Specie did not germinate for some reason.                         

                                      TABLE V-B                                   __________________________________________________________________________    Post-Emergence Multi-Weed Herbicide Test                                      Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________    24B 35 25 45  60 65  85 90  100 100 -- 90 100                                                                              65  --                           88B 60 30 30  90 100 80 100 100 100 100                                                                              30 100                                                                              20  100                          89B 50 70 35  90 60  35 20  100 90  100                                                                              35 100                                                                              15  100                          90B 30 100                                                                              40  100                                                                              70  10 25  100 100 100                                                                              30 90 50  95                           103B                                                                              95 100                                                                              70  100                                                                              65  75 65  100 100 100                                                                              65 100                                                                              50  100                          104B                                                                              30 100                                                                              40  100                                                                              70  10 25  100 100 100                                                                              30 90 50  95                           __________________________________________________________________________     (--) = Specie did not germinate for some reason.                         

                                      TABLE VI-B                                  __________________________________________________________________________    Pre-Emergence Multi-Weed Herbicide Test                                       Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No.  DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                          __________________________________________________________________________     1B  25 10 30  85  55 0  --  55  --  100                                                                              -- 75 75  35                          23B  55 95 90  100                                                                               95*                                                                              95 95  98  80  -- 10 100                                                                              95  --                          68B  65 100                                                                              60  100                                                                               100*                                                                             6  90  100 90  100                                                                              20 100                                                                              30  40                          69B  70 100                                                                              60  100                                                                               100*                                                                             95 95  100 95  100                                                                              0  100                                                                              85  25                          70B  60 100                                                                              75  100                                                                               100*                                                                             85 100 100 90  100                                                                              25 100                                                                              90  25                          76B  100                                                                              100                                                                              85  100                                                                               100*                                                                             85 98  100 95  -- 35 100                                                                              95                              78B  40 70 15  95  75*                                                                              25 80  65  75  -- 0  100                                                                              80  --                          79B  100                                                                              100                                                                              100 100                                                                              100 98 100 100 85  100                                                                              85 100                                                                              95  --                          80B  98 100                                                                              95  100                                                                              100 60 98  99  90  100                                                                              35 100                                                                              85  --                          83B  20 100                                                                              60  100                                                                               100*                                                                             40 90  85  65  100                                                                              0  100                                                                              85  --                          84B  0  90 25  98  100*                                                                             30 90  20  35  100                                                                              5  100                                                                              50  --                          85B  80 100                                                                              50  100                                                                              100 60 90  100 90  100                                                                              0  100                                                                              95  --                          86B  60 90 40  100                                                                              100 60 70  35  60  100                                                                              100                                                                              100                                                                              --  --                          87B  0  90 15  100                                                                               85 15 70  40  60  100                                                                              40 90 20  --                          92B  20 40 10  95  40 10 60  65  30  100                                                                              0  55 60  0                           93B  60 95 20  100                                                                              100 75 100 100 100 100                                                                              0  100                                                                              40  35                          94B  0  80 40  100                                                                               95 25 85  80  40  100                                                                              10 85 55  10                          95B  98 100                                                                              30  100                                                                              100 40 90  100 100 100                                                                              40 100                                                                              90  30                          96B  100                                                                              100                                                                              75  100                                                                              100 95 100 100 100 100                                                                              60 100                                                                              85  100                         97B  100                                                                              100                                                                              90  100                                                                              100 95 100 100 100 100                                                                              60 100                                                                              95  100                         98B  95 100                                                                              100 100                                                                              100 80 100 100 100 100                                                                              50 100                                                                              100 60                           99B**                                                                             -- 100                                                                              75  100                                                                               100*                                                                             20 75  50  75  95 0  -- 85  30                          100B 100                                                                              98 98  100                                                                              100 90 95  100 75  100                                                                              70 100                                                                              95  40                          102B 0  100                                                                              25  100                                                                               90 75 95  60  60  100                                                                              30 100                                                                              90  --                          __________________________________________________________________________     *seedling johnsongrass (Sroghum halepense) was substituted for roxorgange     sorghum.                                                                      **Application rate was 0.56 kg/ha                                             (--) = Specie did not germinate for some reason.                         

                                      TABLE VII-B                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicide Test                                      Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No.  DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                          __________________________________________________________________________     1B  45 35 40  90 35  10 --  60  --  75 -- 60 50  55                          23B  90 100                                                                              80  90  90*                                                                              90 90  80  90  90 40 70 25  --                          68B  50 60 40  85  80*                                                                              75 100 95  90  85 55 100                                                                              40  --                          69B  70 80 35  90  90*                                                                              80 90  80  85  90 20 90 25  --                          70B  100                                                                              90 80  100                                                                              100*                                                                              95 100 100 95  80 30 75 45  90                          76B  100                                                                              100                                                                              98  100                                                                              100*                                                                              100                                                                              100 100 100 100                                                                              60 100                                                                              40  --                          78B  100                                                                              90 80  85 100*                                                                              70 90  100 100 100                                                                              0  90 45  --                          79B  80 35 45  70  60*                                                                              70 70  45  98  100                                                                              35 90 20  --                          80B  60 70 25  90  60*                                                                              60 85  70  90  100                                                                              15 100                                                                              25  100                         85B  95 100                                                                              65  100                                                                              80  90 100 100 100 100                                                                              25 100                                                                              85  --                          86B  30 60 20  75 50  50 60  50  65  100                                                                              10 100                                                                              20  80                          87B  0  0  0   100                                                                              45  20 30  60  90  80 0  100                                                                              30  45                          92B  20 80 10  85 15  0  30  100 40  100                                                                              0  60 60  30                          93B  70 100                                                                              25  100                                                                              100 85 100 100 100 100                                                                              100                                                                              100                                                                              80  --                          94B  20 70 30  90 80  30 20  100 100 100                                                                              60 30 30  100                         95B  60 90 15  95 95  25 90  100 100 100                                                                              75 100                                                                              70  100                         96B  50 80 0   90 70  30 100 100 100 100                                                                              40 100                                                                              20  100                         97B  65 100                                                                              35  100                                                                              75  70 80  100 100 100                                                                              50 100                                                                              50  100                         98B  95 100                                                                              65  95 90  100                                                                              95  100 100 90 40 80 60  95                           99B**                                                                             -- 100                                                                              95  90  90*                                                                              90 100 25  80  40 100                                                                              -- 35  75                          100B 65 75 60  80 75  60 85  100 100 100                                                                              45 100                                                                              65  60                          102B 30 75 20  80 60  0  40  70  100 100                                                                              30 100                                                                              75  --                          __________________________________________________________________________     *Seedling johnsongram (Sorghum halepense) was substituted for roxorange       sorghum.                                                                      **Application rate was 0.56 kg/ha.                                            (--) = Specie did not germinate for some reason.                         

                                      TABLE IV-C                                  __________________________________________________________________________    Post-Emergence Multi-weed Herbicidal Test                                     Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________    2C  0  100                                                                              0   100                                                                              --  45 70  65  50  100                                                                              15 100                                                                              90  --                           __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE V-C                                   __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate - 1.12 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________    2D  0  30 0   100                                                                              --  0  60  85  95  100                                                                              100                                                                              90 40  --                           __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE IV-D                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate - 2.24 kg/ha                                                 Cmpd.                                                                         No. DB FT ARG WG SHC WO BSG AMG SESB                                                                              VL SP MD YNS CB                           __________________________________________________________________________     7D 100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 100 100                                                                              100                                                                              100                                                                              95  100                           8D 100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 100 100                                                                              100                                                                              100                                                                              95  --                           16D.sup.a                                                                         70 100                                                                              65  100                                                                              100 60 98  55  100 100                                                                              90 100                                                                              90  --                           24D 100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 100 100                                                                              100                                                                              100                                                                              100 --                           29D 100                                                                              100                                                                              100 100                                                                              100 100                                                                              100 100 100 100                                                                              30 100                                                                              95  80                           33D 75 15 60  90 90  20 95  100 100 100                                                                              60 100                                                                              95  100                          53D 100                                                                              100                                                                              100 100                                                                              100 90 100 100 100 100                                                                              100                                                                              100                                                                              95  100                          57D 100                                                                              100                                                                              25  100                                                                              100 30 25  100 100 100                                                                              100                                                                              100                                                                              95  100                          64D.sup.a                                                                         -- 0  0   95 35  0  15  50  75  75 25 -- 75  40                           66D.sup.a                                                                         -- 0  15  15 50  20 50  100 100 75 0  -- 90  100                          67D.sup.a                                                                         -- 0  0   100                                                                              100 0  25  95  75  50 25 -- 30  75                           69D.sup.a                                                                         -- 30 0   100                                                                              100 0  70  100 100 100                                                                              35 -- 95  100                          70D.sup.a                                                                         -- 100                                                                              10  100                                                                              100 25 65  100 100 100                                                                              0  -- 95  100                          __________________________________________________________________________     (--) = Not tested.                                                            .sup.a Tested at 0.28 kg/ha.                                             

                                      TABLE V-D                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate-1.12 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    34D 90 85 30  95 -- 45 98 75  100 100                                                                              40 100                                                                              50 --                              35D 100                                                                              85 70  100                                                                              -- 90 100                                                                              100 100 100                                                                              40 100                                                                              75 --                              40D 100                                                                              100                                                                              20  100                                                                              -- 70 100                                                                              98  98  100                                                                              20 100                                                                              50 --                              41D 100                                                                              100                                                                              80  100                                                                              -- 60 100                                                                              100 100 100                                                                              25 100                                                                              95 --                              42D 50 60 40  85 -- 30 100                                                                              100 100 100                                                                              100                                                                              100                                                                              90 --                              43D 90 95 60  100                                                                              -- 30 98 100 98  100                                                                              45 100                                                                              95 --                              44D 60 100                                                                              20  100                                                                              -- 60 100                                                                              100 90  100                                                                              20 100                                                                              80 --                              45D 95 100                                                                              35  100                                                                              -- 60 90 100 100 100                                                                              0  100                                                                              90 --                              46D 100                                                                              100                                                                              90  100                                                                              -- 95 100                                                                              100 100 100                                                                              40 100                                                                              95 --                              47D 100                                                                              100                                                                              100 100                                                                              -- 98 100                                                                              100 98  100                                                                              30 100                                                                              95 --                              48D 100                                                                              100                                                                              100 100                                                                              -- 100                                                                              100                                                                              100 100 100                                                                              90 100                                                                              100                                                                              --                              49D 100                                                                              100                                                                              100 100                                                                              -- 100                                                                              100                                                                              100 100 100                                                                              90 100                                                                              -- --                              50D 100                                                                              100                                                                              100 100                                                                              100                                                                              85 100                                                                              100 100 100                                                                              90 100                                                                              98 --                              54D 100                                                                              100                                                                              85  100                                                                              100                                                                              15 100                                                                              25  100 100                                                                              65 100                                                                              95 100                             55D 85 100                                                                              35  100                                                                              98 15 100                                                                              15  100 100                                                                              65 100                                                                              95 --                              56D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100                                                                              100                             58D 98 100                                                                              40  95 40 20 95 100 100 100                                                                              85 100                                                                              100                                                                              95                              59D 100                                                                              100                                                                              100 100                                                                              100                                                                              90 100                                                                              100 100 100                                                                              100                                                                              100                                                                              85 80                              60D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              75 100                                                                              85 80                              __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE VI-D                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate-0.56 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    61D -- 100                                                                              65  100                                                                              65 20 80 20  40  80 10 -- 20 0                               62D -- 50 35  70 50 0  0  0   25  50 0  -- 0  0                               63D 100                                                                              100                                                                              100 100                                                                              100                                                                              95 100                                                                              90  95  100                                                                              75 100                                                                              100                                                                              85                              68D -- 0  20  0  0  0  0  60  100 100                                                                              90 -- 75 75                              71D -- 50 40  50 75 40 35 75  50  70 0  -- 75 75                              72D -- 35 60  100                                                                              85 50 100                                                                              25  65  100                                                                              35 -- 100                                                                              35                              73D -- 90 70  100                                                                              95 25 0  70  100 100                                                                              0  -- 50 25                              __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE VII-D                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate-2.24 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________     7D 100                                                                              100                                                                              100 100                                                                              80 90 10 95  100 100                                                                              55 100                                                                              45 100                             16D.sup.a                                                                         100                                                                              85 35  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              85 70                              24D 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100                                                                              --                              29D 100                                                                              100                                                                              60  100                                                                              90 100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100                                                                              --                              33D 90 98 85  100                                                                              100                                                                              80 100                                                                              100 100 100                                                                              90 100                                                                              90 100                             53D 100                                                                              100                                                                              60  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              100                                                                              --                              57D 25 40 10  100                                                                              10 0  10 100 95  100                                                                              35 100                                                                              -- 100                             64D.sup.a                                                                         -- 0  0   90 0  0  85 40  100 80 50 -- 35 100                             66D.sup.a                                                                         -- 0  0   65 0  0  70 75  80  75 0  -- 25 75                              67D.sup.a                                                                         -- 0  0   75 35 0  40 70  80  60 0  -- 0  100                             69D.sup.a                                                                         -- 0  0   80 35 0  100                                                                              90  100 100                                                                              40 -- 35 100                             70D.sup.a                                                                         -- 100                                                                              0   100                                                                              70 90 90 100 100 100                                                                              30 -- 25 100                             __________________________________________________________________________     (--) = Not tested.                                                            .sup.a Tested at 0.28 kg/ha.                                             

                                      TABLE VIII-D                                __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate-1.12 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    34D 90 85 30  95 -- 45 98 75  100 100                                                                              40 100                                                                              50 --                              35D 100                                                                              85 70  100                                                                              -- 90 100                                                                              100 100 100                                                                              40 100                                                                              75 --                              40D 75 100                                                                              5   100                                                                              -- 50 75 100 100 100                                                                              40 100                                                                              30 --                              41D--                                                                             -- -- --  -- -- -- -- --  --  -- -- -- -- --                              42D 40 100                                                                              35  100                                                                              -- 50 80 100 100 100                                                                              80 100                                                                              70 --                              43D 60 70 20  100                                                                              -- 55 60 100 100 100                                                                              95 100                                                                              70 --                              44D -- -- --  -- -- -- -- --  --  -- -- -- -- --                              45D -- -- --  -- -- -- -- --  --  -- -- -- -- --                              46D -- -- --  -- -- -- -- --  --  -- -- -- -- --                              47D 90 100                                                                              35  100                                                                              -- 75 90 100 100 100                                                                              25 100                                                                              45 --                              48D 80 100                                                                              60  100                                                                              -- 60 80 100 100 100                                                                              85 100                                                                              60 --                              49D -- -- --  -- -- -- -- --  --  -- -- -- -- --                              50D 90 80 60  95 80 90 100                                                                              100 100 100                                                                              65 100                                                                              80 --                              54D 35 50 30  100                                                                              30 15 90 100 100 100                                                                              100                                                                              100                                                                              95 --                              55D 100                                                                              100                                                                              20  100                                                                              90 20 100                                                                              90  100 100                                                                              100                                                                              100                                                                              -- --                              56D 75 90 75  95 90 25 100                                                                              100 100 100                                                                              90 100                                                                              90 100                             58D 70 100                                                                              40  100                                                                              95 30 95 100 95  100                                                                              95 100                                                                              95 85                              59D 90 100                                                                              95  100                                                                              100                                                                              50 100                                                                              100 100 100                                                                              95 100                                                                              100                                                                              95                              60D 95 100                                                                              100 100                                                                              100                                                                              75 95 100 100 100                                                                              95 100                                                                              100                                                                              100                             __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE IX-D                                  __________________________________________________________________________    Post-Emergence Multi-weed Herbicide Test                                      Application Rate-0.56 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG SHC                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    61D -- 40 0   50 35 0  40 75  95  100                                                                              0  -- 25 50                              62D -- 35 0   20 0  0  20 35  60  100                                                                              0  -- 0  100                             63D 100                                                                              100                                                                              85  98 85 100                                                                              100                                                                              100 100 100                                                                              100                                                                              85 85 95                              68D -- 30 40  85 0  25 60 80  95  100                                                                              95 -- 0  80                              71D -- 50 0   80 65 0  75 100 80  100                                                                              50 -- 25 100                             72D -- 90 70  80 50 50 75 85  100 100                                                                              90 -- 100                                                                              100                             73D -- 100                                                                              15  100                                                                              75 75 85 100 100 90 60 -- 80 100                             __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE IV-E                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate-2.24 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                 __________________________________________________________________________    17E 95 85 35  100                                                                              85                                                                              25 90 100 100 100                                                                              40 100                                                                              95                                  18E 0  0  0   50 20                                                                              0  15 60  45  100                                                                              0  100                                                                              --                                  __________________________________________________________________________

                                      TABLE V-E                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate-1.12 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                __________________________________________________________________________     7E 30 70 20  100                                                                              75 0  90 100 95  100                                                                              100                                                                              100                                                                              90                                  8E 95 95 45  100                                                                              98 25 90 100 95  100                                                                              90 100                                                                              90                                  9E 10 70 40  100                                                                              20 0  80 100 85  100                                                                              40 100                                                                              95                                 10E 100                                                                              100                                                                              10  100                                                                              40 0  90 100 100 100                                                                              80 100                                                                              100                                11E 90 100                                                                              90  100                                                                              100                                                                              65 100                                                                              100 90  100                                                                              30 100                                                                              65                                 12E 100                                                                              100                                                                              80  100                                                                              100                                                                              85 90 100 100 100                                                                              85 100                                                                              90                                 13E 0  100                                                                              10  100                                                                              100                                                                              80 70 80  90  100                                                                              70 100                                                                              80                                 15E 0  10 0   90 0  0  15 35  30  100                                                                              10 85 75                                 19E 100                                                                              90 0   100                                                                              20 10 40 95  100 100                                                                              100                                                                              100                                                                              65                                 __________________________________________________________________________

                                      TABLE VI-E                                  __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate-2.24 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG                                                                              WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                 __________________________________________________________________________    17E 80 100                                                                              55  95 90                                                                              20 60 100 100 100                                                                              75 100                                                                              70                                  18E 0  100                                                                              0   98 20                                                                              0  10 70  60  100                                                                              10 100                                                                              45                                  __________________________________________________________________________

                                      TABLE VII-E                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate-1.12 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                __________________________________________________________________________     7E 25 30 0   70 60 20 90 75  95  85 50 100                                                                              35                                  8E 80 80 20  70 70 40 80 50  80  80 60 60 35                                  9E 0  30 0   75 15 25 100                                                                              95  100 100                                                                              60 100                                                                              25                                 10E 60 80 20  70 35 25 80 75  90  90 70 100                                                                              45                                 11E 45 100                                                                              20  100                                                                              100                                                                              40 50 100 100 100                                                                              20 100                                                                              35                                 12E 70 60 30  100                                                                              100                                                                              80 98 90  100 100                                                                              70 98 40                                 13E 25 100                                                                              10  100                                                                              100                                                                              85 100                                                                              80  100 100                                                                              10 90 25                                 15E 30 65 10  90 50 30 20 85  80  98 30 65 15                                 19E 20 60 10  90 10 15 90 100 100 70 100                                                                              40 85                                 __________________________________________________________________________

                                      TABLE IV-F                                  __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate-1.12 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    19F 40 35 60  100                                                                              90 30 90 100 100 -- 20 100                                                                              90 --                              26F 25 70 45  95 60 25 85 35  75  -- 20 100                                                                              95 90                              27F 45 65 40  100                                                                              60 25 80 100 85  100                                                                              40 100                                                                              95 35                              28F 80 100                                                                              90  100                                                                              100                                                                              90 100                                                                              70  90  100                                                                              30 100                                                                              95 35                              29F 90 45 75  100                                                                              85 40 90 95  90  100                                                                              40 100                                                                              95 --                              30F 90 45 75  100                                                                              90 75 100                                                                              100 80  100                                                                              60 100                                                                              95 --                              31F 60 65 75  100                                                                              100                                                                              55 95 100 100 100                                                                              100                                                                              100                                                                              95 --                              32F 90 100                                                                              90  100                                                                              100                                                                              65 85 100 90  100                                                                              95 100                                                                              85 --                              33F 100                                                                              100                                                                              95  100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              25 100                                                                              90 --                              35F 90 100                                                                              100 100                                                                              -- 90 90 100 90  100                                                                              10 100                                                                              75 --                              36F 90 35 85  100                                                                              -- 15 80 95  90  100                                                                              50 100                                                                              95 --                              39F 100                                                                              100                                                                              100 100                                                                              100                                                                              95 100                                                                              100 100 100                                                                              100                                                                              100                                                                              98 --                              40F 100                                                                              100                                                                              80  100                                                                              100                                                                              70 100                                                                              100 100 100                                                                              90 100                                                                              95 --                              41F 100                                                                              100                                                                              100 100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              60 100                                                                              98 --                              42F 60 100                                                                              85  100                                                                              100                                                                              70 95 100 95  100                                                                              10 100                                                                              95 50                              43F 85 100                                                                              25  100                                                                              60 25 98 100 100 100                                                                              100                                                                              100                                                                              90 100                             44F 0  80 10  85 0  0  75 0   30  100                                                                              0  100                                                                              0  10                              45F 25 100                                                                              40  100                                                                              60 0  65 60  60  100                                                                              50 100                                                                              70 0                               50F -- 100                                                                              50  100                                                                              35 35 75     100 100                                                                              --                                       __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE V-F                                   __________________________________________________________________________    Pre-Emergence Multi-weed Herbicide Test                                       Application Rate-0.56 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    46F 0  65 35  75 65 0  0  0   35  100                                                                              25 90 80 0                               47F -- 60 35  100                                                                              100                                                                              0  90 100 100 100                                                                              70 -- 100                                                                              75                              48F -- 75 20  90 60 0  15 70  35  90 0  -- 20 40                              49F -- 60 10  100                                                                              60 0  50 100 95  100                                                                              40 -- 90 100                             51F -- 40 10  95 40 10 50 65  100 100                                                                              0  -- 95 65                              __________________________________________________________________________     (--)-Not tested.                                                         

                                      TABLE VI-F                                  __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate-2.24 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    19F 100                                                                              90 65  100                                                                              100                                                                              98 100                                                                              100 100 100                                                                              60 100                                                                              70 100                             26F 60 75 60  95 45 50 90 50  90  100                                                                              40 90 60 --                              27F 80 70 65  95 100                                                                              90 100                                                                              100 100 100                                                                              85 100                                                                              75 --                              28F 80 100                                                                              75  90 85 80 100                                                                              80  80  100                                                                              30 100                                                                              85 85                              29F 85 70 55  90 98 90 100                                                                              100 100 100                                                                              35 100                                                                              60 100                             30F 90 80 40  .90                                                                              85 80 80 70  100 100                                                                              20 100                                                                              40 --                              31F 100                                                                              80 20  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              85 --                              32F 70 90 60  100                                                                              100                                                                              98 100                                                                              100 100 100                                                                              100                                                                              100                                                                              60 --                              33F 95 100                                                                              80  100                                                                              90 100                                                                              100                                                                              100 100 100                                                                              70 100                                                                              40 --                              35F 70 90 40  100                                                                              -- 100                                                                              100                                                                              100 100 100                                                                              98 100                                                                              30 --                              36F 85 100                                                                              35  100                                                                              -- 20 100                                                                              100 100 100                                                                              100                                                                              100                                                                              15 --                              39F 100                                                                              100                                                                              85  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              100                                                                              100                                                                              90 100                             40F 100                                                                              100                                                                              30  100                                                                              100                                                                              100                                                                              100                                                                              100 100 100                                                                              90 100                                                                              75 --                              41F 100                                                                              100                                                                              35  90 70 100                                                                              90 100 100 100                                                                              50 100                                                                              70 --                              42F 45 100                                                                              50  100                                                                              70 55 80 100 100 100                                                                              70 100                                                                              75 100                             43F 25 80 15  98 35 0  20 100 100 100                                                                              100                                                                              100                                                                              60 95                              44F 0  15 0   65 0  0  0  70  100 100                                                                              40 100                                                                              0  100                             45F 0  75 35  70 35 0  60 50  85  100                                                                              50 100                                                                              75 70                              50F -- 40 0   75 45 40 60 100 100 95 30 -- 60 100                             __________________________________________________________________________     (--) = Not tested.                                                       

                                      TABLE VII-F                                 __________________________________________________________________________    Post-Emergence Multi-Weed Herbicidal Activity                                 Application Rate-0.56 kg/ha                                                   Cmpd.                                                                         No. DB FT ARG WG JG WO BSG                                                                              AMG SESB                                                                              VL SP MD YNS                                                                              CB                              __________________________________________________________________________    46F 25 35 20  50 35 35 0  20  75  100                                                                              35 95 -- 50                              47F -- 75 25  90 40 25 80 100 100 100                                                                              80 -- 75 100                             48F -- 50 35  80 35 40 0  75  100 85 15 -- 50 75                              49F -- 35 0   75 30 0  20 100 100 100                                                                              80 -- 25 85                              51F -- 35 0   80 35 20 70 50  95  95 25 -- 65 50                              __________________________________________________________________________     (--) = Not Tested.                                                       

The compounds of the present invention and their salts are useful asherbicides and can be applied in a variety of ways at variousconcentrations. In practice, the compounds or salts are formulated intoherbicidal compositions, by admixture, in herbicidally effectiveamounts, with the adjuvants and carriers normally employed forfacilitating the dispersion of active ingredients for agriculturalapplications, recognizing the fact that the formulation and mode ofapplication of a toxicant may affect the activity of the materials in agiven application. Thus, these active herbicidal compounds or salts canbe formulated as granules of relatively large particle size, as wettablepowders, as emulsifiable concentrates, as powdery dusts, as flowables,as solutions or as any of several other known types of formulations,depending upon the desired mode of application. These formulations maycontain as little as about 0.5% to as much as about 95% or more byweight of active ingredient. A herbicidally effective amount dependsupon the nature of the seeds or plants to be controlled and the rate ofapplication varies from about 0.01 to approximately 10 pounds per acre,preferably from about 0.02 to about 4 pounds per acre.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersants. The wettable powder isultimately applied to the soil either as a dry dust or as a dispersionin water or other liquid. Typical carriers for wettable powders includefuller's earth, kaolin clays, silicas and other readily wet organic orinorganic diluents. Wettable powders normally are prepared to containabout 5% to about 95% of the active ingredient and usually also containa small amount of wetting, dispersing, or emulsifying agent tofacilitate wetting and dispersion.

Emulsifiable concentrates are homogeneous liquid compositions which aredispersible in water or other dispersant, and may consist entirely ofthe active compound or salt with a liquid or solid emulsifying agent, ormay also contain a liquid carrier, such as xylene, heavy aromaticnaphthal, isophorone and other non-volatile organic solvents. Forherbicidal application, these concentrates are dispersed in water orother liquid carrier and normally applied as a spray to the area to betreated. The percentage by weight of the essential active ingredient mayvary according to the manner in which the composition is to be applied,but in general comprises about 0.5% to 95% of active ingredient byweight of the herbicidal composition.

Granular formulations wherein the toxicant is carried on relativelycoarse particles, are usually applied without dilution to the area inwhich suppression of vegetation is desired. Typical carriers forgranular formulations include sand, fuller's earth, attapulgite clay,bentonite clays, montmorillonite clay, vermiculite, perlite and otherorganic or inorganic materials which absorb or which may be coated withthe toxicant. Granular formulations normally are prepared to containabout 0.1% to about 25% of active ingredients which may includesurface-active agents such heavy aromatic naphthas, kerosene or otherpetroleum fractions, or vegetable oils; and/or stickers such asdextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents and adjuvants used inagricultural formulations include, for example, the alkyl and alkylarylsulfonates and sulfates and their salts; polyhydric alcohols;polyethoxylated alcohols, esters and fatty amines; and other types ofsurface-active agents, many of which are available in commerce. Thesurface-active agent, when used, normally comprises from 0.1% to 30% byweight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient withfinely divided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers for the toxicant,are useful formulations for soil-incorporating application.

Pastes, which are homogeneous suspensions of a finely divided solidtoxicant in a liquid carrier such as water or oil, are employed forspecific purposes. These formulations normally contain about 5% to about95% of active ingredient by weight, and may also contain small amountsof a wetting, dispersing or emulsifying agent to facilitate dispersion.For application, the pastes are normally diluted and applied as a sprayto the area to be affected.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a dispersant in which it iscompletely soluble at the desired concentration, such as water, acetone,alkylated naphthalenes, xylene and other organic solvents. Pressurizedsprays, typically aerosols, wherein the active ingredient is dispersedin finely-divided form as a result of vaporization of a low boilingdispersant solvent carrier, such as the Freons, may also be used.

The phytotoxic compositions of this invention can be applied to theplants in the conventional manner. Thus, the dust and liquidcompositions can be applied to the plant by the use of power-dusters,boom and hand sprayers and spray dusters. The compositions can also beapplied from airplanes as a dust or a spray or by rope wick applicationsbecause they are effective in very low dosages. In order to modify orcontrol growth of germinating seeds or emerging seedlings, as a typicalexample, the dust and liquid compositions can be applied to the soilaccording to conventional methods and can be distributed in the soil toa depth of at least 1/2 inch below the soil surface. It is not necessarythat the phytotoxic compositions be mechanically admixed with the soilparticles since these compositions can also be applied merely byspraying or sprinkling the surface of the soil. The phytotoxiccompositions of this invention can also be applied by addition toirrigation water supplied to the field to be treated. This method ofapplication permits the penetration of the compositions into the soil asthe water is absorbed therein. Dust compositions, granular compositionsor liquid formulations applied to the surface of the soil can bedistributed below the surface of the soil by conventional means such asdiscing, dragging or mixing operations. In the following examples theherbicidal compound can be substituted with the herbicidal salt of thecompound.

    __________________________________________________________________________    General Formula with Ranges                                                                     Specific Formula                                            __________________________________________________________________________    EMULSIFIABLE CONCENTRATE FORMULATIONS                                         Herbicidal compound                                                                       5-55  herbicidal compound                                                                        24                                             surfactant(s)                                                                             5-25  proprietary blend of oil-                                                                  10                                             solvent(s) 20-90  soluble sulfonates and                                                 100%   polyoxyethylene ethers                                                        polar solvent                                                                              27                                                               petroleum hydrocarbon                                                                      39                                                                            100%                                           WETTABLE POWDER FORMULATIONS                                                  herbicidal compound                                                                       3-90  herbicidal compound                                                                        80                                             wetting agent                                                                            0.5-2  sodium dialkyl naphthalene                                                                 0.5                                            dispersing agent                                                                         1-8    sulfonate                                                   diluent(s) 8.5-87 sodium lignosulfonate                                                                      7                                                         100%   attapulgite clay                                                                           12.5                                                                          100%                                           EXTRUDED GRANULAR FORMULATIONS                                                herbicidal compound                                                                       1-20  herbicidal compound                                                                        10                                             binding agent                                                                             0-10  lignin sulfonate                                                                           5                                              diluent(s) 70-99  calcium carbonate                                                                          85                                                        100%                100%                                           FLOWABLE FORMULATIONS                                                         herbicidal compound                                                                      20-70  herbicidal compound                                                                        45                                             surfactant(s)                                                                             1-10  polyoxyethylene ether                                                                      5                                              suspending agent(s)                                                                      0.05-1 attagel      0.05                                           antifreeze agent                                                                          1-10  propylene glycol                                                                           10                                             antimicrobial agent                                                                       1-10  1,2-benzisothiazoline-3-one                                                                0.03                                           antifoam agent                                                                           0.1-1  silicone defoamer                                                                          0.02                                           solvent     7.95-77.85                                                                          water        39.9                                                      100%                100%                                           __________________________________________________________________________

When salts are used as the active ingredient in the herbicidalcompositions of this invention it is recommended to use salts that areagriculturally acceptable.

The phytotoxic compositions of this invention can also contain otheradditives, for example, fertilizers, other herbicides and otherpesticides, used as adjuvant or in combination with any of theabove-described adjuvants. Fertilizers useful in combination with theactive ingredients include, for example, ammonium nitrate, urea andsuperphosphate.

We claim:
 1. Compounds having the structural formula ##STR96## wherein R₃ is methoxy or ethoxy andR₄ is bromine, methylsulfonyl or ethylsulfonyl and their salts.
 2. A method of controlling undesireable vegetation comprising applying to the area where control is desired an herbicidally effective amount of a compound having the structural formula ##STR97## wherein R₃ is methoxy or ethoxy andR₄ is bromine, methylsulfonyl or ethylsulfonyl and their salts.
 3. An herbicidal composition comprising an herbicidally effective amount of a compound having the structural formula ##STR98## wherein R₃ is methoxy or ethoxy andR₄ is bromine, methylsulfonyl or ethylsulfonyl and their salts and an inert carrier therefor. 